DD228248A1 - PROCESS FOR SYNTHESIS OF PYRAZOLES - Google Patents
PROCESS FOR SYNTHESIS OF PYRAZOLES Download PDFInfo
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- DD228248A1 DD228248A1 DD26918984A DD26918984A DD228248A1 DD 228248 A1 DD228248 A1 DD 228248A1 DD 26918984 A DD26918984 A DD 26918984A DD 26918984 A DD26918984 A DD 26918984A DD 228248 A1 DD228248 A1 DD 228248A1
- Authority
- DD
- German Democratic Republic
- Prior art keywords
- mmol
- diphenyl
- triphenylphosphine
- pyrazole
- colorless
- Prior art date
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- 150000003217 pyrazoles Chemical class 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 title claims description 5
- 238000003786 synthesis reaction Methods 0.000 title claims description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 38
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 amino, hydrazino Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004442 acylamino group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 2
- 125000003282 alkyl amino group Chemical group 0.000 claims 1
- 239000003495 polar organic solvent Substances 0.000 claims 1
- 150000008338 1,3,4-thiadiazines Chemical class 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 230000002048 spasmolytic effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000010626 work up procedure Methods 0.000 description 6
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VYNGFCUGSYEOOZ-UHFFFAOYSA-N triphenylphosphine sulfide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=S)C1=CC=CC=C1 VYNGFCUGSYEOOZ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZFVJLNKVUKIPPI-UHFFFAOYSA-N triphenyl(selanylidene)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=[Se])C1=CC=CC=C1 ZFVJLNKVUKIPPI-UHFFFAOYSA-N 0.000 description 2
- JSBYEVFXBCOJDR-UHFFFAOYSA-N (4,5-diphenyl-1h-pyrazol-3-yl)hydrazine Chemical compound NNC1=NNC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 JSBYEVFXBCOJDR-UHFFFAOYSA-N 0.000 description 1
- UGFGYIGBEMDDFJ-UHFFFAOYSA-N (E)-(5,6-diphenyl-3,6-dihydro-1,3,4-thiadiazin-2-ylidene)hydrazine Chemical compound S1C(NN)=NN=C(C=2C=CC=CC=2)C1C1=CC=CC=C1 UGFGYIGBEMDDFJ-UHFFFAOYSA-N 0.000 description 1
- FVRXOULDGSWPPO-UHFFFAOYSA-N 1,2-dihydropyrazole-3-thione Chemical class SC1=CC=NN1 FVRXOULDGSWPPO-UHFFFAOYSA-N 0.000 description 1
- JVVRJMXHNUAPHW-UHFFFAOYSA-N 1h-pyrazol-5-amine Chemical class NC=1C=CNN=1 JVVRJMXHNUAPHW-UHFFFAOYSA-N 0.000 description 1
- LGZPFIZZYQNDIC-UHFFFAOYSA-N 2,5,6-triphenyl-6h-1,3,4-thiadiazine Chemical compound S1C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=NN=C1C1=CC=CC=C1 LGZPFIZZYQNDIC-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- LCEPTUJTFRDIKL-UHFFFAOYSA-N 2-benzyl-5,6-diphenyl-6h-1,3,4-thiadiazine Chemical compound C=1C=CC=CC=1CC(S1)=NN=C(C=2C=CC=CC=2)C1C1=CC=CC=C1 LCEPTUJTFRDIKL-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
- JWPUMLMBTPMEQA-UHFFFAOYSA-N 4,5-diphenyl-1h-pyrazol-3-amine Chemical compound NC1=NNC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 JWPUMLMBTPMEQA-UHFFFAOYSA-N 0.000 description 1
- NREKSYYMXSKUEY-UHFFFAOYSA-N 5,6-diphenyl-6h-1,3,4-thiadiazin-2-amine Chemical compound S1C(N)=NN=C(C=2C=CC=CC=2)C1C1=CC=CC=C1 NREKSYYMXSKUEY-UHFFFAOYSA-N 0.000 description 1
- LXKATDBAGISYLC-UHFFFAOYSA-N 5-benzyl-3,4-diphenyl-1h-pyrazole Chemical compound C=1C=CC=CC=1CC=1NN=C(C=2C=CC=CC=2)C=1C1=CC=CC=C1 LXKATDBAGISYLC-UHFFFAOYSA-N 0.000 description 1
- CPAJUUHSPXQIEO-UHFFFAOYSA-N 6H-1,3,4-selenadiazine Chemical class [Se]1C=NN=CC1 CPAJUUHSPXQIEO-UHFFFAOYSA-N 0.000 description 1
- KPVWENBMDKKORU-UHFFFAOYSA-N C(C)(C)(C)NC1=NNC(=C1C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C(C)(C)(C)NC1=NNC(=C1C1=CC=CC=C1)C1=CC=CC=C1 KPVWENBMDKKORU-UHFFFAOYSA-N 0.000 description 1
- XGUCUZZJIJUTDC-UHFFFAOYSA-N C1CCCCN1C1=NN=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)S1 Chemical compound C1CCCCN1C1=NN=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)S1 XGUCUZZJIJUTDC-UHFFFAOYSA-N 0.000 description 1
- KUJMHIIIPDSLKF-UHFFFAOYSA-N C1COCCN1C1=NN=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)S1 Chemical compound C1COCCN1C1=NN=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)S1 KUJMHIIIPDSLKF-UHFFFAOYSA-N 0.000 description 1
- FZYAEBMOPXENKM-UHFFFAOYSA-N N,5,6-triphenyl-3,6-dihydro-1,3,4-selenadiazin-2-imine Chemical compound N(C1=NN=C(C([Se]1)c1ccccc1)c1ccccc1)c1ccccc1 FZYAEBMOPXENKM-UHFFFAOYSA-N 0.000 description 1
- TVVSXMBQGWUSON-UHFFFAOYSA-N N-tert-butyl-5,6-diphenyl-3,6-dihydro-1,3,4-selenadiazin-2-imine Chemical compound [Se]1C(NC(C)(C)C)=NN=C(C=2C=CC=CC=2)C1C1=CC=CC=C1 TVVSXMBQGWUSON-UHFFFAOYSA-N 0.000 description 1
- CCKOKCQLYMGWRD-UHFFFAOYSA-N N1(CCCCC1)C1=NNC(=C1C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound N1(CCCCC1)C1=NNC(=C1C1=CC=CC=C1)C1=CC=CC=C1 CCKOKCQLYMGWRD-UHFFFAOYSA-N 0.000 description 1
- AJAAXRIDGCLEOB-UHFFFAOYSA-N N=1N(C)C(=NC(C)C)SC(C=2C=CC=CC=2)C=1C1=CC=CC=C1 Chemical compound N=1N(C)C(=NC(C)C)SC(C=2C=CC=CC=2)C=1C1=CC=CC=C1 AJAAXRIDGCLEOB-UHFFFAOYSA-N 0.000 description 1
- ZUIPSQCXLXSXTN-UHFFFAOYSA-N O1CCN(CC1)C1=NNC(=C1C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound O1CCN(CC1)C1=NNC(=C1C1=CC=CC=C1)C1=CC=CC=C1 ZUIPSQCXLXSXTN-UHFFFAOYSA-N 0.000 description 1
- IGFUIIWDBWTTCW-UHFFFAOYSA-N S1C(NC(C)(C)C)=NN=C(C=2C=CC=CC=2)C1C1=CC=CC=C1 Chemical compound S1C(NC(C)(C)C)=NN=C(C=2C=CC=CC=2)C1C1=CC=CC=C1 IGFUIIWDBWTTCW-UHFFFAOYSA-N 0.000 description 1
- NNUVWYYIGPJNLB-UHFFFAOYSA-N S1C(NC)=NN=C(C=2C=CC=CC=2)C1C1=CC=CC=C1 Chemical compound S1C(NC)=NN=C(C=2C=CC=CC=2)C1C1=CC=CC=C1 NNUVWYYIGPJNLB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- YJLGCXPZNGJSNA-UHFFFAOYSA-N n,4,5-triphenyl-1h-pyrazol-3-amine Chemical compound C=1C=CC=CC=1NC1=NNC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 YJLGCXPZNGJSNA-UHFFFAOYSA-N 0.000 description 1
- WNCBOCHZYFLGLB-UHFFFAOYSA-N n,n-dimethyl-4,5-diphenyl-1h-pyrazol-3-amine Chemical compound CN(C)C1=NNC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 WNCBOCHZYFLGLB-UHFFFAOYSA-N 0.000 description 1
- CXWJBKQTLMTFNP-UHFFFAOYSA-N n-methyl-4,5-diphenyl-1h-pyrazol-3-amine Chemical compound CNC1=NNC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 CXWJBKQTLMTFNP-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012262 resinous product Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
Abstract
Die Erfindung betrifft ein Verfahren zur Herstellung substituierter Pyrazole. Die Titelverbindungen sind als Pharmaka mit spasmolytischer Wirksamkeit einsetzbar und koennen als organische Zwischenprodukte verwendet werden. Sie lassen sich erfindungsgemaess in guten Ausbeuten aus in 6-Stellung substituierten 1,3,4-Thiadiazinen bzw. 1,3,4-Selenadiazinen durch Erhitzen in organischen Loesungsmitteln in Gegenwart von Triphenylphosphin bzw. Triethyl-phosphit darstellen.The invention relates to a process for the preparation of substituted pyrazoles. The title compounds can be used as drugs with spasmolytic activity and can be used as organic intermediates. According to the invention, they can be prepared in good yields from 1,3,4-thiadiazines or 1,3,4-seleno-diazines substituted in the 6-position by heating in organic solvents in the presence of triphenylphosphine or triethylphosphite.
Description
-Λ--Λ-
a) Titel der Erfindunga) Title of the invention
Verfahren zur Synthese von PyrazolenProcess for the synthesis of pyrazoles
b) Anwendungsgebiet der Erfindungb) Field of application of the invention
Die Erfindung betrifft ein Verfahren zur Herstellung substituierter Pyrazole, die hinsichtlich der spasmolytischen Eigenschaften und als organische Zwischenprodukte von Interesse sind·The invention relates to a process for the preparation of substituted pyrazoles which are of interest with regard to spasmolytic properties and as organic intermediates.
c) Charakteristik: der bekannten technischen Lösungen Es ist bekannt, daß sich 3-Amino-pyrazole aus Acylacetonitrilen und Hydrazinen (0· Seidel, J. prakt· Chem. [2] 5§, (1898) 129, C. Alberti, Gazz. Chim. Ital. 82, (1959) 1017) herstellen lassen. 3-Alkylamino- bzw. 3-Aryl amino-5-phenyl-pyrazole erhält man aus ß-Morpholinothiozimtsäure-Ii-alkyl(aryl)-amiden und Hydrazinen (H· Beyer, H. Honeck und R· Reichelt, Liebigs Ann. Chem· 741 (1970) 45» S. Hünig und K. Hübner, Chem. Ber. 95 (1962) 937)· H. Beyer et al. und J. Sandström beobachteten unabhängig voneinander eine unter Abscheidung von elementarem Schwefel verlaufende Ringverengung von 6H-1,3>4-Thiadiazinen zu Pyrazolen (H. Beyer und G. Wolter, Chem. Ber. 82 (1956) 1652; J. Sandström, Ark. Eemi 8 (1956) 523)· Diese Entschwefelungsreaktionen der 1,3,.4-Thiadiazine können in Gegenwart von Säuren durchgeführt werden, so z. B. durch Erhitzen in Eisessig in ethanolischer Salzsäure bzw. konz. Salzsäure oder Bromwasserstoffsäure (vgl. H. Beyer, Z. Chem. _9 (1969) 361; W.D. Pfeiffer,c) Characteristics: known technical solutions It is known that 3-amino-pyrazoles are obtained from acylacetonitriles and hydrazines (0 · Seidel, J. prakt. Chem. [2] 5§, (1898) 129, C. Alberti, Gazz Chim. Ital. 82, (1959) 1017). 3-Alkylamino- or 3-aryl-amino-5-phenyl-pyrazoles are obtained from .beta.-morpholinothiozimic acid-1-alkyl (aryl) -amides and hydrazines (H. Beyer, H. Honeck and R. Reichelt, Liebigs Ann. Chem · 741 (1970) 45 »S. Hünig and K. Huebner, Chem. Ber. 95 (1962) 937) · H. Beyer et al. and J. Sandström independently observed a ring narrowing of 6H-1,3> 4-thiadiazines to pyrazoles proceeding under the deposition of elemental sulfur (H. Beyer and G. Wolter, Chem. Ber. 82 (1956) 1652; J. Sandström, Ark. Eemi 8 (1956) 523). These desulfurization reactions of 1,3, .4-thiadiazines can be carried out in the presence of acids, such. B. by heating in glacial acetic acid in ethanolic hydrochloric acid or conc. Hydrochloric acid or hydrobromic acid (see H. Beyer, Z. Chem., 9 (1969) 361; WD Pfeiffer,
E. DiIk und E. Bulka, Wiss. Zeitschrift der Ernst-E. DiIk and E. Bulka, Wiss. Journal of Serious
Moritz-Arndt-Üniversität XXVII (1978) 135 und dort zitierte Literatur). Aber auch mit Basen wie Natriumethanolat (W.D. Pfeiffer, E, DiIk und E. Bulka, Synthesis 1977 196), Natriumhydroxid (W.D.- Pfeiffer und E. Bulka, DDE-Patent WP 0 07 D/244 624/7) > Butyllithium (E.R. Schmidt und E. Hutht Tetrahedron Letters London 1975« 33; W.D. Pfeiffer, K. Geisler, H. Roßberg und E. Bulks-, Z. Chem. 22 (1982) 137) werden 1,3,4-Thiadiazine in Pyrazole überführt. Bei der Einwirkung von thiophilen Phosphor-Verbindungen auf in 6-iStellung unsubstituierte 1,3,4-Thiadiazine erhält man ein Reaktionsgemisch aus S-freien Pyrazolen und 3-Mercaptopyrazolen, die teilweise oder vollständig zu Dipyrazolyl-(4,4»)- <3isalfiden oxidiert werden (WiD. Pfeiffer und E. Bulka, Synthesis 1977« 485). Bei diesem Syntheseverfahren wird jedoch die Isolierung der S-freien Pyrazole durch die gebildeten Hebenprodukte erschwert·Moritz-Arndt University XXVII (1978) 135 and literature cited therein). But also with bases such as sodium ethanolate (WD Pfeiffer, E, DiIk and E. Bulka, Synthesis 1977 196), sodium hydroxide (WD-Pfeiffer and E. Bulka, DDE patent WP 0 07 D / 244 624/7)> Butyllithium (ER Schmidt and E. Hutht Tetrahedron Letters London 1975 "33; WD Pfeiffer, K. Geisler, H. Rossberg and E. Bulks, Z. Chem. 22 (1982) 137) converted 1,3,4-thiadiazines into pyrazoles. The action of thiophilic phosphorus compounds on unsubstituted in 6-i position 1,3,4-thiadiazines to obtain a reaction mixture of S-free pyrazoles and 3-mercaptopyrazoles, which partially or completely to Dipyrazolyl- (4,4 ») - < 3isalfides are oxidized (WiD Pfeiffer and E. Bulka, Synthesis 1977 485). In this synthesis method, however, the isolation of the S-free pyrazoles by the lifting products formed is made difficult ·
d) Ziel der Erfindungd) Object of the invention
Die Erfindung hat das Ziel, ein neues Verfahren zur Herstellung von 3-Amino-, 3-Hydrazino-, 3-Alkyl(aryl)amino-, 3-Aryl- und 3-Alkyl-pyrazole aus 1,3,4-Thiadiazinen und 1 >3»4-~Selenadiazinen zu entwickeln,, bei dem keine Nebenreaktionen auftreten.The invention has the goal of a new process for the preparation of 3-amino, 3-hydrazino, 3-alkyl (aryl) amino, 3-aryl and 3-alkyl-pyrazoles from 1,3,4-thiadiazines and 1> 3 »4- ~ to develop selenadiazines, in which no side reactions occur.
e) Darlegung des Wesens und der Merkmale der Erfindung Erfindungsgemäß iaerden Pyrazole der allgemeinen Formeln dargestellt,e) DESCRIPTION OF THE NATURE AND THE FEATURES OF THE INVENTION According to the invention, pyrazoles of the general formulas are represented,
wobei R eine Aryl-, Benzyl-, Amino-, Hydrazino-, Alkyl-where R is an aryl, benzyl, amino, hydrazino, alkyl
2 amino-, Arylamino-, Dialkylamino- oder Acylaminogruppe R und R-^ einen Arylrest oder eine niedere geradkettige oder2 amino, arylamino, dialkylamino or acylamino group R and R ^ an aryl radical or a lower linear or
verzweigte Alkylgruppe und R einen niederen geradkettigen oder verzweigten AlkyIrest bedeuten, indem man in 6-Stellung substituierte 6H-1,3,4-Thiadiazine bzw. 6H-1,3,4-Selenadiazine in polaren oder unpolaren organischen Lösungsmitteln in Gegenwart von Triphenylphosphin bzw. Triethylphosphit auf Temperaturen von 50 - 160 0C erhitzt.branched alkyl group and R is a lower straight-chain or branched AlkyIrest by 6-substituted-6H-1,3,4-thiadiazines or 6H-1,3,4-selenadiazines in polar or nonpolar organic solvents in the presence of triphenylphosphine or Triethyl phosphite to temperatures of 50 - 160 0 C heated.
f) Ausführungsbeispielef) embodiments
3-Methylamino-4,5-diphenyl-pyrazol3-methylamino-4,5-diphenyl-pyrazole
2,81 g (10 mmol) 2-Methylamino-5,6-diphenyl-6H-1,3,4-thiadiazin und 2,62 g (10 mmol) Triphenylphosphin werden in. 60 ml n-Butanol 3 Std. unter Rückfluß erhitzt. Beim Abkühlen scheidet sich Triphenylphosphinsulfid ab, das abgesaugt und aus: Ethanol umkristallisiert wird, F. 160,5 °C· Das Filtrat der Umsetzung versetzt man mit 1 ml konz. Salzsäure und läßt es in Ether eintropfen. Hierbei scheidet sich das 3-Methylamino-4,-5-diphenyl-pyra,zol-hydrochlorid ab. Die freie Base erhält man aus der ethanolischen Lösung des Hydrochlorids durch Zugabe von Ammoniak. Ausb. 2,06 g (.83 %). Farblose Blättchen (aus Ethanol), F. 176 0C.2.81 g (10 mmol) of 2-methylamino-5,6-diphenyl-6H-1,3,4-thiadiazine and 2.62 g (10 mmol) of triphenylphosphine are refluxed in 60 ml of n-butanol for 3 hours heated. Upon cooling, triphenylphosphine separates out, which is filtered off and recrystallized from: ethanol, mp 160.5 ° C. The filtrate of the reaction is mixed with 1 ml of conc. Hydrochloric acid and allowed to drip into ether. Here, the 3-methylamino-4, -5-diphenyl-pyra, zol hydrochloride separates out. The free base is obtained from the ethanolic solution of the hydrochloride by adding ammonia. Y. 2.06 g (.83%). Colorless Leaflets (from ethanol), mp 176 ° C.
3-n-Propylamino-4,5-diphenyl-pyrazol3-n-propylamino-4,5-diphenyl-pyrazole
a) 3»O9 g (10 mmol) 2-n-Propylamino-5,6-diphenyl-6H-1,3,4-thiadiazin und 2,62 g (10 mmol) Triphenylphosphin werden in 50 ml n-Butanol 3 Std. unter Rückfluß erhitzt. Weitere Aufarbeitung analog Beispiel 1. Ausb. 2,24 g (81 %). Farblose Nadeln (aus Benzen/Petrolether), F.. 181 0C.a) 3 »O9 g (10 mmol) of 2-n-propylamino-5,6-diphenyl-6H-1,3,4-thiadiazine and 2.62 g (10 mmol) of triphenylphosphine are dissolved in 50 ml of n-butanol for 3 hrs heated under reflux. Further workup analogous to Example 1. Ausb. 2.24 g (81%). Colorless needles (from benzene / petroleum ether), F .. 181 0 C.
b) 3i56 g (10 mmol) 2-n-Propylamino-5,6-diphenyl-6H-1,3,4-selenadiazin und 2,62 g (10 mmol) Triphenylphosphinb) 3i56 g (10 mmol) of 2-n-propylamino-5,6-diphenyl-6H-1,3,4-selenadiazine and 2.62 g (10 mmol) of triphenylphosphine
werden in 50 ml n-Butanol 4 Std. unter Rückfluß erhitzt. Beim Kühlen in Eis scheidet sich ein niederschlag von Triphenylphosphinselenid ab. Farblose Stäbchen (aus Ethanol), F· 185 - 186 0C. (Lit. H. Michaelis und H. v. Soden, Liebigs Ann. Ghem. 22£ (1885) 308, F. 183 184 0G). Weitere Aufarbeitung analog Beispiel 1. Ausb* 2,3 g (83 %). Farblose ladeIn (aus Benzen/Petrolether), F. 181 0O.are refluxed in 50 ml of n-butanol for 4 hrs. When cooling in ice, a precipitate separates from triphenylphosphine selenide. Colorless rods (from ethanol), F · 185-186 0 C. (Lit. H. Michaelis and H. v Soden, Liebigs Ann Ghem 22 £ (1885) 308 F. 183 184 0 G...). Further work-up analogously to Example 1. Yield * 2.3 g (83%). Colorless Charging In (from benzene / petroleum ether), m.p. 181 0 O.
3-t ert · Butylamino-4,5-diphe nyl-pyra zo 13-tert-butylamino-4,5-diphenylpyrazole zo 1
a) 3,23 g (10 mmol) 2-tert.Butylamino-5,6-diphenyl-6H-1,3,4-thiadiazin und 2,62 g (10 mmol) Triphenylphosphin werden in 30 ml Toluen 2 Std. unter Rückfluß erhitzt. Beim Abkühlen scheidet sich Triphenylphosphiasulfid ab, das abgesaugt wird. Yom Filtrat werden 15 ml Toluen abdestilliert. Man kühlt in %s, wobei das Pyrazol auskristallisiert. Ausb. 2,62 g (90 %). Farblose Stäbchen (aus Ethanol), F. 211 - 212 0G.a) 3.23 g (10 mmol) of 2-tert-butylamino-5,6-diphenyl-6H-1,3,4-thiadiazine and 2.62 g (10 mmol) of triphenylphosphine in 30 ml of toluene for 2 hr. Under Reflux heated. Upon cooling, triphenyl phosphine sulfide separates out, which is sucked off. From the filtrate 15 ml of toluene are distilled off. It is cooled in% s, the pyrazole crystallized out. Y. 2.62 g (90 %) . Colorless rods (from ethanol), m.p. 211-212 0 G.
ti) 3»70 g (10 mmol) 2-tert.Butylamino-5,6-diphenyl-6H-1,3,4-selenadiazin und 2,62 g (10 mmol) Triphenylphosphin werden in 40 ml Toluen 3 Std. unter Rückfluß erhitzt. Nach" Abtrennung des Triphenylphosphinselenids werden vom Filtrat 20 ml Toluen abdestilliert. Beim Abkühlen in Eis scheidet sich das Pyrazol ab. Ausb. 2,5 g (86 %)· Farblose Stäbchen (aus Ethanol), F. 211 - 212 0G.ti) 3 »70 g (10 mmol) of 2-tert-butylamino-5,6-diphenyl-6H-1,3,4-selenadiazine and 2.62 g (10 mmol) of triphenylphosphine are in 40 ml of toluene for 3 hr. Under Reflux heated. 212 0 G. - by "separation of Triphenylphosphinselenids 20 ml of toluene 2.5 g (86%) · Colorless rods (from ethanol), m.p. 211 are distilled off from the filtrate upon cooling in ice, the pyrazole separates y...
3-Anilino-4,5-diphenyl-pyrazol3-anilino-4,5-diphenyl-pyrazole
a) 3»43 S (10 mmol) 2-Anilino-5,6-diphenyl-6H-1,3>4-thiadiazin und 2,62 g (10 mmol·) Triphenylphosphin werden in 80 ml n-Butanol 6 Std. unter Rückfluß erhitzt. Weitere Aufarbeitung analog Beispiel 1. Ausb* 2,8 g (90 %)· Farblose Nadeln (aus Benzen), F. 182 0C'.a) 3 »43 S (10 mmol) of 2-anilino-5,6-diphenyl-6H-1,3> 4-thiadiazine and 2.62 g (10 mmol ·) of triphenylphosphine are dissolved in 80 ml of n-butanol for 6 hours. heated to reflux. Further work-up analogously to Example 1. Yield * 2.8 g (90%). · Colorless needles (from benzene), mp 182 ° C.
b) 3,90 g (10 mmol) 2-Anilino-5,6-diphenyl-6H-1,3,4-selenadiazin und 2,62 g (10 mmol) Triphenylphosphin werden in 60 ml Toluen 9 Std. unter Rückfluß erhitzt. Nach Abtrennung des Triphenylphosphinselenids werden vom Filtrat 40 ml Toluen abdestilliert. Beim Kühlen in %s scheidet sich das Pyrazol ab. Ausb. 2,7 g (87 %). Farblose Nadeln (aus Benzen), F. 182 0C.b) 3.90 g (10 mmol) of 2-anilino-5,6-diphenyl-6H-1,3,4-selenadiazine and 2.62 g (10 mmol) of triphenylphosphine are refluxed in 60 ml of toluene for 9 hours , After separation of the triphenylphosphine selenide, 40 ml of toluene are distilled off from the filtrate. When cooling in% s, the pyrazole separates out. Y. 2.7 g (87 %) . Colorless needles (from benzene), mp 182 0 C.
3-Dimethylamino-4,5-diphenyl-pyrazol 2,95 g (10 mmol) 2-Dimethylamino-5,6-diphenyl-6H-1,3*4-thiadiazin und 1,66 g (10 mmol) Triethyl-phosphit werden in 50 ml Benzen 10 Std. unter Rückfluß erhitzt. Anschließend werden. 30 ml des Lösungsmittels abdestilliert. Beim Abkühlen scheidet sich das Pyrazol ab· Ausb. 2,11 g (80 %). Farblose Blättchen (aus Ethanol), F. 202 - 203 0O.3-Dimethylamino-4,5-diphenyl-pyrazole 2.95 g (10 mmol) of 2-dimethylamino-5,6-diphenyl-6H-1,3 * 4-thiadiazine and 1.66 g (10 mmol) of triethyl phosphite are refluxed in 50 ml benzene for 10 hrs. Then be. Distilled off 30 ml of the solvent. Upon cooling, the pyrazole separates out · Ausb. 2.11 g (80%). Colorless platelets (from ethanol), mp 202 - 203 0 O.
3-Piperidino-4,5-diphenyl-pyrazol3-piperidino-4,5-diphenyl-pyrazole
3,35 S (10 mmol) 2-Piperidino-5,6-diphenyl-6H-1,3,4-thiadiazin und 2,62 g (10 mmol) Triphenylphosphin werden in 30 ml Ethanol 8 Std. unter Rückfluß erhitzt. Aufarbeitung analog Beispiel 1· Ausb· 2,7 g (89 %)· Farblose Nadeln (aus Ethanol), F. 207 0C3.35 S (10 mmol) of 2-piperidino-5,6-diphenyl-6H-1,3,4-thiadiazine and 2.62 g (10 mmol) of triphenylphosphine are refluxed in 30 ml of ethanol for 8 hours. Working up analogously to Example 1 · Yield · 2.7 g (89%) · Colorless needles (from ethanol), mp 207 ° C.
3-Morpholino-4,5-diphenyl-pyrazol3-morpholino-4,5-diphenyl-pyrazole
Aus 3,37 g (10 mmol) 2-Morpholino-5,6-diphenyl-6H-1,3,4-thiadiazin und 2,62 g (10 mmol) Triphenylphosphin wie beim Beispiel 6 beschrieben. Ausb· 2,7 g (87 %)· Farblose Nadeln (aus Ethanol), F. 222 0C.From 3.37 g (10 mmol) of 2-morpholino-5,6-diphenyl-6H-1,3,4-thiadiazine and 2.62 g (10 mmol) of triphenylphosphine as described in Example 6. Yield · 2.7 g (87 %) · Colorless needles (from ethanol), mp 222 ° C.
3-Amino-4,5-diphenyl-pyrazol3-amino-4,5-diphenyl-pyrazole
Aus 2,67 S (10 mmol) 2-Amino-5,6-diphenyl-6H-1,3,4-thiadiazin und 2,62 g (10 mmol) Triphenylphosphin analog Beispiel 1. Ausb. 2,0 g (85 %). Farblose Prismen (aus Trichlorethylen), F. 146 0G.From 2.67 S (10 mmol) of 2-amino-5,6-diphenyl-6H-1,3,4-thiadiazine and 2.62 g (10 mmol) of triphenylphosphine analogously to Example 1. Yield. 2.0 g (85%). Colorless prisms (from trichlorethylene), mp 146 0 G.
Beispiel JlOjLExample J10J
3-Hydrazino-4,5-diphenyl-pyrazol3-hydrazino-4,5-diphenyl-pyrazole
Aus 2,82 g (10 mmol) 2-Hydrazino-5,6-diphenyl-6H-1,3,4-thiadiazin analog Beispiel 1. Ausb. 2,0 g (80 %). Farblose Blättchen (aus Ethanol), P. 181 0C.From 2.82 g (10 mmol) of 2-hydrazino-5,6-diphenyl-6H-1,3,4-thiadiazine analogously to Example 1. Ausb. 2.0 g (80%). Colorless leaflets (ethanol), P. 181 0 C.
3-Anilino-4-methyl-5-phenyl-pyrazol 2,81 g (10 mmol) 2-Anilino-5-phenyl-6-methyl-6H-1,3,4-thiadiazin und 2,62 g (10 mmol) Triphenylphosphin werden in 20 ml Toluen 24 Std. unter Rückfluß erhitzt. Man destilliert 10 ml Toluen ab. Beim Abkühlen scheidet sich ein Gemisch aus Iriphenylphosphinsulfid und Pyrazol ab. Man löst in warmem Ethanol. Das beim Abkühlen ausfallende Triphenylphosphinsulfid wird abfiltriert. Aufarbeitung analog Beispiel 1. Ausb. 1,79 g (72 %). Farblose Blättchen (aus Trichlorethylen), F. 140 0C.3-Anilino-4-methyl-5-phenyl-pyrazole 2.81 g (10 mmol) of 2-anilino-5-phenyl-6-methyl-6H-1,3,4-thiadiazine and 2.62 g (10 mmol ) Triphenylphosphine are refluxed in 20 ml toluene for 24 hrs. Distilled 10 ml of toluene. Upon cooling, a mixture of iriphenylphosphine sulfide and pyrazole separates out. Dissolve in warm ethanol. The precipitated during cooling Triphenylphosphinsulfid is filtered off. Work-up analogous to Example 1. Ausb. 1.79 g (72%). Colorless leaflets (of trichlorethylene), mp 140 ° C.
3-Anilino-4-ethyl-5-phenyl-pyrazol3-anilino-4-ethyl-5-phenyl-pyrazole
Aus 2,95 S (10 mmol) 2-Anilino-5-phenyl-6-methyl-6H-1 ,3,4-thiadiazin analog Beispiel 11. Äusb. 1,84 g (70 %). Farblose Nadeln (aus verd. Ethanol), F. I27 0O.From 2.95 S (10 mmol) of 2-anilino-5-phenyl-6-methyl-6H-1,3,4-thiadiazine analogously to Example 11. Ex. 1.84 g (70%). Colorless needles (from dilute ethanol), F. I27 0 O.
3^inino-4-metl^l-5-pheir/l-pyrazol-hydrochlorid 2,05 g (10 mmol) 2^Amino-5-methyl-6-phenyl-6H-1,3,4-thiadiazin und 2,62 g (10 mmol) Triphenylphosphin werden in 20 ml Ethanol 15 Std. unter Rückfluß erhitzt. Nach dem Abkühlen saugt man die ausgefallenen Kristalle von Triphenyl phosphinsulfid ab. Ausb. 3,7 g (63 %). Das Lösungsmittel wird i. Yak. abdestilliert und der Rückstand mit Wasser ausgekocht. Geringe Mengen eines zurückbleibenden harzigen Produktes werden verworfen. Insgesamt.wird die Substanz dreimal aus Wasser umkristallisiert. Anschließend trocknet man über -P^O10 bei 50 0C. Die Substanz wird in Ether gelöst und durch Einleiten von Salzsäuregas das Hydrchlorid ausgefällt. Ausb. 1,2 g (61 %). Farblose unregelmäßige3-amino-4-methyl-1-5-phenyl / 1-pyrazole hydrochloride 2.05 g (10 mmol) of 2-amino-5-methyl-6-phenyl-6H-1,3,4-thiadiazine and 2 , 62 g (10 mmol) of triphenylphosphine are refluxed in 20 ml of ethanol for 15 hours. After cooling, the precipitated crystals of triphenyl phosphine sulfide are filtered off with suction. Y. 3.7 g (63%). The solvent is i. Yak. distilled off and the residue boiled with water. Small amounts of a residual resinous product are discarded. Gesamt.wird the substance is recrystallized three times from water. Then it is dried over -P ^ O 10 at 50 0 C. The substance is dissolved in ether and precipitated by passing hydrochloric acid gas, the hydrochloride. Y. 1.2 g (61%). Colorless irregular
Prismen, F. 176 - 177 0C (Zers.).Prisms, F. 176 - 177 0 C (Zers.).
Beispiel 14-: -Example 14-:
3-Ainino-4--ei:hyl-5-plien7l-pyrazol-hydrochlorid Aus 2,19 g (10 mmol) 2-Amino-5-phenyl-6-ethyl-6H-1,3,4-thiadiazin und 2,62 g (10 mmol) Tripheny !phosphin in 40 ml Ethanol wie bei Beispiel 13 beschrieben. Fach dem Umkristallisieren aus Wasser erhält man das Monohydrat des 3-AmirLO-4-ethyl-5-phenyl-pyrazols in farblose Fädeln, P. 80 - 81 0C. Ausb. 1,4 g (68 %). Anschließend wird über P^P-io ^ei ^0 °C getrocknet und das amorphe Produkt durch Lösen in Ether und Einleiten von Salzsäuregas in das gut kristalline Hydrochlorid überführt. Ausb. 1,45 g (65 %). Farblose Blättchen, F. 171 - 172 0C (Zers.).3-Aynino-4-eyl-5-plien-7-pyrazole hydrochloride From 2.19 g (10 mmol) of 2-amino-5-phenyl-6-ethyl-6H-1,3,4-thiadiazine and 2 , 62 g (10 mmol) Tripheny! Phosphine in 40 ml ethanol as described in Example 13. Subject to recrystallization from water gives the monohydrate of 3-AmirLO-4-ethyl-5-phenyl-pyrazole in colorless threads, P. 80 - 81 0 C. Ausb. 1.4 g (68%). The mixture is then dried over P ^ P-io ^ ei ^ 0 ° C and the amorphous product is converted by dissolving in ether and passing hydrochloric acid gas into the well-crystalline hydrochloride. Y. 1.45 g (65%). Colorless Leaflets, F. 171 - 172 0 C (dec.).
3,4,5-T?iphenyl-pyrazol3,4,5-T? Iphenyl-pyrazole
Aus 3,28 g (10 mmol) 2,5,6-Triphenyl-6H-1,3,4-thiadiazin und 2,62 g (10 mmol) Triphenylphosphin werden in 30 ml Toluen 3 Std. unter Rückfluß erhitzt. Aufarbeitung analog Beispiel 4. Ausb. 2,46 g (83 %). Farblose Fädeln (aus Ethanol). F. 269 - 270 0C.From 3.28 g (10 mmol) of 2,5,6-triphenyl-6H-1,3,4-thiadiazine and 2.62 g (10 mmol) of triphenylphosphine are refluxed in 30 ml of toluene for 3 hrs. Work-up analogous to Example 4. Ausb. 2.46 g (83%). Colorless threads (made of ethanol). F. 269 - 270 0 C.
Beispiel 'IjSt1 Example IjSt 1
3-Benzyl-4,5-diphenyl-pyrazol3-Benzyl-4,5-diphenyl-pyrazole
Aus 3,42 g (10 mmol) 2-Benzyl-5,6-diphenyl-6H-1,3,4-thiadiazin analog Beispiel 4. Ausb. 2,7 g (87 %). Farblose Fädeln (aus Ethanol), F. 172 0C.From 3.42 g (10 mmol) of 2-benzyl-5,6-diphenyl-6H-1,3,4-thiadiazine analogously to Example 4. Ausb. 2.7 g (87%). Colorless threads (from ethanol), mp 172 0 C.
1-Methy1-3,4-diphenyl-5-isopropylamino-pyrazol1-Methy1-3,4-diphenyl-5-isopropylamino-pyrazol
a) 3,23 g (10 mmol) 2-Isopropylimino-3-methyl-5,6-diphenyl 2,3-dihydro-6H-1,3,4-thiadiazin und 2,62 g (10 mmol) Triphenylphosphin werden in 3ü ml n-Butanol 24 Std. unter Rückfluß erhitzt. Aufarbeitung analog Beispiel 1. Ausb. 2,4 g (82 %). Farblose Stäbchen (aus verd. Ethanol), F. 88 0C.a) 3.23 g (10 mmol) of 2-isopropylimino-3-methyl-5,6-diphenyl 2,3-dihydro-6H-1,3,4-thiadiazine and 2.62 g (10 mmol) of triphenylphosphine are in 3 ml of n-butanol is refluxed for 24 hours. Work-up analogous to Example 1. Ausb. 2.4 g (82%). Colorless rod (diluted from. Ethanol), mp 88 0 C.
"b) 3»7O g (10 ffimol) 2-Isopropylimino-3-niethyl-5>6-diphenyl-2,3-dihydro-6H-1,3>4-selenadiazin und 2,62 g (10 mmol) Triphenylphosphin werden in 40 ml n-Butanol 28 Std. unter Rückfluß erhitzt. Aufarbeitung analog wie bei Beispiel 2 unter b) beschrieben. Ausb. 2,3 g (79 %)· Farblose Stäbchen (aus verd. Ethanol), F. 88 0C."b) 3" 7O g (10 mmole) of 2-isopropylimino-3-niethyl-5>6-diphenyl-2,3-dihydro-6H-1,3> 4-selenadiazine and 2.62 g (10 mmole) of triphenylphosphine 28 h. Working up in 40 ml of n-butanol heated to reflux. analogously as described in example 2 b). Yield. 2.3 g (79%) · Colorless rods (from dil. ethanol), mp C 88 0 ,
Claims (2)
oder Acylaminogruppe R und-1Br eine Arylgruppe oder einen niederen geradkettigen oder verzweigten Alkylrest und R einen.niederen geradkettigen oder verzweigten Alkylrest bedeuten. 2 1
or acylamino group R and - 1 Br is an aryl group or a lower straight-chain or branched alkyl radical and R is a lower straight-chain or branched alkyl radical.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD26918984A DD228248A1 (en) | 1984-11-07 | 1984-11-07 | PROCESS FOR SYNTHESIS OF PYRAZOLES |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD26918984A DD228248A1 (en) | 1984-11-07 | 1984-11-07 | PROCESS FOR SYNTHESIS OF PYRAZOLES |
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| Publication Number | Publication Date |
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| DD228248A1 true DD228248A1 (en) | 1985-10-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6028068A (en) * | 1995-12-28 | 2000-02-22 | The Procter & Gamble Company | Substituted 6H-1,3,4-thiadiazine-2-amines, the use thereof as anaesthetising, cardiovascular and hypometabolic agents, and a pharmaceutical composition containing them |
| US6313111B1 (en) | 1995-12-28 | 2001-11-06 | The Procter & Gamble Company | Substituted 6H-1,3,4-thiadiazine-2-amines, the use thereof as anaesthetising, cardiovascular and hypometabolic agents, and pharmaceutical composition containing them |
-
1984
- 1984-11-07 DD DD26918984A patent/DD228248A1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6028068A (en) * | 1995-12-28 | 2000-02-22 | The Procter & Gamble Company | Substituted 6H-1,3,4-thiadiazine-2-amines, the use thereof as anaesthetising, cardiovascular and hypometabolic agents, and a pharmaceutical composition containing them |
| US6313111B1 (en) | 1995-12-28 | 2001-11-06 | The Procter & Gamble Company | Substituted 6H-1,3,4-thiadiazine-2-amines, the use thereof as anaesthetising, cardiovascular and hypometabolic agents, and pharmaceutical composition containing them |
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