DE2311510A1 - PROCESS FOR THE PREPARATION OF 1-HYDRAZINO-PHTHALAZINE.HYDROCHLORIDE - Google Patents
PROCESS FOR THE PREPARATION OF 1-HYDRAZINO-PHTHALAZINE.HYDROCHLORIDEInfo
- Publication number
- DE2311510A1 DE2311510A1 DE19732311510 DE2311510A DE2311510A1 DE 2311510 A1 DE2311510 A1 DE 2311510A1 DE 19732311510 DE19732311510 DE 19732311510 DE 2311510 A DE2311510 A DE 2311510A DE 2311510 A1 DE2311510 A1 DE 2311510A1
- Authority
- DE
- Germany
- Prior art keywords
- hydrazino
- palladium
- hydrochloric acid
- phthalazine
- process according
- Prior art date
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title claims description 3
- RPTUSVTUFVMDQK-UHFFFAOYSA-N Hidralazin Chemical compound C1=CC=C2C(NN)=NN=CC2=C1 RPTUSVTUFVMDQK-UHFFFAOYSA-N 0.000 title description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 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 description 3
- ODCNAEMHGMYADO-UHFFFAOYSA-N 1,4-dichlorophthalazine Chemical compound C1=CC=C2C(Cl)=NN=C(Cl)C2=C1 ODCNAEMHGMYADO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- ZUXNZUWOTSUBMN-UHFFFAOYSA-N hydralazine hydrochloride Chemical compound Cl.C1=CC=C2C(NN)=NN=CC2=C1 ZUXNZUWOTSUBMN-UHFFFAOYSA-N 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 1,2-disubstituted benzene Chemical class 0.000 description 1
- KGLPWQKSKUVKMJ-UHFFFAOYSA-N 2,3-dihydrophthalazine-1,4-dione Chemical compound C1=CC=C2C(=O)NNC(=O)C2=C1 KGLPWQKSKUVKMJ-UHFFFAOYSA-N 0.000 description 1
- OEIOKPQWHXSUCH-UHFFFAOYSA-N 3-amino-3h-2-benzofuran-1-one Chemical compound C1=CC=C2C(N)OC(=O)C2=C1 OEIOKPQWHXSUCH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WTYSCLHDMXBMKM-UHFFFAOYSA-N phthalazin-1-amine Chemical class C1=CC=C2C(N)=NN=CC2=C1 WTYSCLHDMXBMKM-UHFFFAOYSA-N 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical class C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000948 sympatholitic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von 1-Hydrazino-phthalazin.Hydrochlorid Process for the production of 1- Hydrazino-phthalazin.Hydroch l orid
(Priorität.: 20. Juli 1972 - Jugoslawien - P 1833/72)(Priority: July 20, 1972 - Yugoslavia - P 1833/72)
Die vorliegende Erfindung.betrifft die Herstellung von 1-Hydrazinophthalazin.Hydrochlorid der FormelThe present invention relates to the production of 1-hydrazinophthalazine hydrochloride the formula
H2-HClH 2 -HCl
Diese Verbindung weist eine sympatikolytische Wirkung auf und wird bei der Behandlung von verschiedenartigen Hypertonien angewandt.This compound has a sympatholytic effect and will used in the treatment of various types of hypertension.
Zur Herstellung von 1-Hydrazino-phthalazin.Hydrochlorid wurden bisher mehrere Methoden entwickelt, welche jedoch eine Reihe von Mangeln aufweisen.For the production of 1-hydrazino-phthalazin.Hydrochlorid were previously developed several methods, which, however, have a number of shortcomings.
Die Herstellung geht von kostspieligen, schwer zugänglichen Rohstoffen aus, oder ist auf teure und spezifische Apparaturen angewiesen. Die beschriebenen Verfahren beziehen sich hauptsächlich auf die Reaktionen des Hydrazins mit dem substituierten Phthalazin oder dem 1,2-disubstituierten Benzol.The production is based on costly raw materials that are difficult to access or relies on expensive and specific equipment. The procedures described are mainly related on the reactions of the hydrazine with the substituted phthalazine or 1,2-disubstituted benzene.
Die erste Gruppe stellen die Methoden dar, welche von 1-Halogen-, 1-Mercapto- oder 1-Amino-phthalazinen bzw. ihrer gemeinsamen Ausgangsverbindung Phthalazon ausgehen (Helvetica Chimica Acta 34 (1959), 204j brit.Patent 629 177; USA Patent 2 484 029; Med.Prom. SSSR, 14 (1960) 2, 13-17? Acta Polon.Pharm. 11 (1955), 27; 3ap.Patent 5526 (154) usw. Das Phthalazon wird durch die Reaktion von Phthalaldehydsäure, 3-Broin-phthalid, 3-Amino-phthalid oder Diphthalidylester mit Hydrazinhydrat (Beilsteins Handbuch der org.Chemie 24 12 und E II 24 70) gewonnen. Eine analogeThe first group represents the methods which are used by 1-halogen, 1-mercapto- or 1-aminophthalazines or their common starting compound Running out of phthalazone (Helvetica Chimica Acta 34 (1959), 204j British Patent 629 177; U.S. Patent 2,484,029; Med.Prom. SSSR, 14 (1960) 2, 13-17? Acta Polon, Pharm. 11: 27 (1955); 3ap. Patent 5526 (154) etc. The phthalazone is produced by the reaction of phthalaldehyde acid, 3-broin-phthalide, 3-amino-phthalide or diphthalidyl ester with hydrazine hydrate (Beilstein's Handbook of Org.Chemie 24 12 and E II 24 70). An analog
309885/1391309885/1391
' . 231151Q'. 231151Q
Herstellungsmethode, ausgehend von Phthalaldehydsäure-Derivaten, ist im französischen Patent 1 335 759 und noch-an einigen Literaturstellen beschrieben. Der gemeinsame Mangel all dieser Methoden liegt in der äusserst kostspieligen Herstellung von Phthalaldehydsäure oder deren Derivaten.Production method based on phthalaldehyde acid derivatives, is in French patent 1,335,759 and still-at some References described. The common shortcoming of all of these methods is the extremely costly production of Phthalaldehyde acid or its derivatives.
Ein2technisch ausführbare Art der Herstellung dieser Säure besteht in der Oxydation von ITaphthalen mittels Kaliumpermanganat, wobei man einen sechsfachen ^ewichtsüberschuss des kostspieligen Kaliumpermanganats anwenden muss.There is a technically feasible way of producing this acid in the oxidation of ITaphthalene by means of potassium permanganate, whereby one has to use a six-fold excess by weight of the expensive potassium permanganate.
Die übrigen technisch ausführbaren Synthesen der Ausgangsstoffe wie Phthalid oder Phthalimidin erfordern komplizierte und kostspielige Apparaturen, da die Umsetzungen durch katalytisch^ Hydrierung der entsprechenden Dioxoverbindungen in Druckgefässen ausgeführt werden (Liebigs Annalen der Chemie, 574, 64 (151)·The other technically feasible syntheses of the starting materials such as phthalide or phthalimidine require complicated and expensive ones Apparatus, since the reactions are carried out by catalytic hydrogenation of the corresponding dioxo compounds in pressure vessels (Liebigs Annalen der Chemie, 574, 64 (151)
Die zweite Gruppe der Methoden geht vom 2-uyano-benzaldehyddiacetat (brit. Patent 719 183) oder α,α,α,α' ,α'-Pentachlor-xylol (franz."Patent 1 438 827), dessen Herstellung nicht einfach ist, · aus.The second group of methods is the 2-u-yano benzaldehyddiacetat (Brit. Patent 719,183), or α, α, α, α ', α'-pentachloropropane-xylene (double. "Patent 1,438,827), whose preparation is not easy is, · off.
Es wurde nun gefunden, dass man das i-Hydrazino-phthalazin.Hydrochlorid einfach und in praktisch quantitativer Ausbeute aus dem leicht zugänglichen i-Hydrazino-4-chlor-phthalazin durch die Hydrogenolyse des Halogens erhält, wenn die !!^halogenierung mittels molekularem Wasserstoff in Anwesenheit von Palladium als Katalysator gemäss folgendem HeaktionsschemaIt has now been found that the i-hydrazino-phthalazin.Hydrochlorid easily and in practically quantitative yield from the easily accessible i-hydrazino-4-chlorophthalazine by the Hydrogenolysis of the halogen is obtained when the !! ^ halogenation by means of molecular hydrogen in the presence of palladium as a catalyst according to the following reaction scheme
.HOl.HOl
ausgeführt wird·is performed·
Das Verfahren wird derart ausgeführt, dass das 1-Hydrasino-4-halogeno-phthalazin in Wasser, niederen Alkoholen oder einem anderen vorteilhaften Lösungsmittel gelöst oder dispergiert ■The process is carried out in such a way that the 1-hydrasino-4-halogenophthalazine dissolved or dispersed in water, lower alcohols or another advantageous solvent
3 0 S 8 8 5 / 1 3 9 13 0 S 8 8 5/1 3 9 1
wird und auf kolloidalem oder auf inerte Träger aufgetragenem Palladium in An- oder Abwesenheit von Halogenwasserstoffsäure-Bindemitteln oder, am vorteilhaftesten, unter Zusatz von Salzsäure hydriert wird.and palladium on colloidal or inert support in the presence or absence of hydrohalic acid binders or, most advantageously, is hydrogenated with the addition of hydrochloric acid.
Die Hydrierung wird bei Raumtemperatur und Normaldruck, zur Beschleunigung der Hydrierung auch bei erhöhter Temperatur und Druck, ausgeführt. Es ist überraschend, dass bei einer temperatur von 80°0 und einem Wasserstoffdruck von I5 atm keine Nebenreaktioiien stattfinden, da bekannt ist, dass es unter ähnlichen Bedingungen zu einer- Hydrogenolyse der N-N Bindungen in derartigen Verbindungen kommt (Zymalkovski "Katalytische Hydrierungen im Organisch-chemischen Laboratorium", Ferdinand Enke Verlag Stuttgart, 1965 S. 304-313).The hydrogenation is carried out at room temperature and normal pressure, to accelerate the hydrogenation also at elevated temperature and Pressure done. It is surprising that at a temperature of 80 ° 0 and a hydrogen pressure of 15 atm no side reactions take place because it is known that under similar conditions there is hydrogenolysis of the N-N bonds in such Compounds comes (Zymalkovski "Catalytic Hydrogenations im Organic-chemical laboratory ", Ferdinand Enke Verlag Stuttgart, 1965 pp. 304-313).
Der Ausgangsstoff i-Hydrazino-4-chlor-phthalazin wird gemäss folgendem ReaktionsschemaThe starting material i-hydrazino-4-chlorophthalazine is according to following reaction scheme
erhalten, d.h. durch die Reaktion des Phthalanhydrids mittels ■kydrazin-hydrat wird in eine? 84 %igen Ausbeute das 1,4-Dihydroxyphthalazin erhalten, welches nach Chlorierung in einer 90 %igen Ausbeute das 1,4-Dichlor-phthalazin ergibt. Aus dem derart hergestellten 1,4-Dichlor-phthalazin wird gemäss dem modifizierten Verfahren, beschrieben in Ηϊΐν. Chimica Acta, 34 (1959), 204, das i-Hydrazino-4-chlor-phthalazin synthetisiert. Nach diesem Verfahren wird die Reaktion mit einem achtfachen molaren Überschuss an Hydrazinhydrat ausgeführt. Durch das modifizierte Verfahren, d.h. durch-den Ersatz von 5 &0I ^ydrazin-hydrat durch 1 Mol Ammoniak wird das i-Hydrazino-4-chlor-phthalazin in 90 %iger Ausbeute erhalten.obtained, i.e. through the reaction of the phthalic anhydride with ■ kydrazine hydrate is converted into a? 84% yield of 1,4-dihydroxyphthalazine obtained, which after chlorination gives the 1,4-dichlorophthalazine in a 90% yield. From the so 1,4-dichlorophthalazine produced is modified according to the Procedure described in Ηϊΐν. Chimica Acta, 34 (1959), 204, which synthesizes i-hydrazino-4-chlorophthalazine. To In this process the reaction is carried out with an eight-fold molar excess of hydrazine hydrate. The modified Process, i.e. by-the replacement of 5 & 0I ^ ydrazine hydrate by 1 mol of ammonia is the i-hydrazino-4-chlorophthalazine in 90% yield obtained.
Derageifiäss stellen das erfindungs^-enässe Verfahren so?/ie die Herstellung der Ausgangsstoffe einen technischen Fortschritt ciar,Derageifiäss put the inventive method so? / Ie the Manufacture of the raw materials a technical progress ciar,
309885/13 91309885/13 91
weil die obigen Reaktionen in einfachen Apparaturen, ausgehend von preiswerten Rohstoffen, welche die chemische Industrie in großen Mengen erzeugt, ausführbar sind.because the above reactions proceed in simple apparatus of inexpensive raw materials, which the chemical industry produces in large quantities, can be carried out.
Das erfindungsgemäße Verfahren soll durch folgende Beispiele erläutert werden:The method according to the invention is illustrated by the following examples explained:
,Beispiel 1 * . . ·.-.-. , Example 1 *. . ·.-.-.
Zu einem Gemisch aus 8,3 g (41,5. m Mol) 1,4-Dichlorphthalazin, 85 ml 96 %igen Äthanol und 3,5 ml 25 %igen wässrigen Ammoniak werden bei 600C 7 ml (etwa 140 m Mol) Hydrazin-hydrat zugetropft. Anschließend wird das Gemisch 5 Minuten zum Sieden erhitzt und das i-Hydrazino-4-chlorphthalazin abgesaugt.To a mixture of 8.3 g (41.5. M mol) of 1,4-dichlorophthalazine, 85 ml 96% ethanol and 3.5 ml of 25% aqueous ammonia are m at 60 0 C 7 ml (about 140 mole ) Hydrazine hydrate was added dropwise. The mixture is then heated to boiling for 5 minutes and the i-hydrazino-4-chlorophthalazine is filtered off with suction.
Die Ausbeute beträgt 7,5 g (94 %).The yield is 7.5 g (94 %) .
Das erhaltene Produkt wird in 120 ml Methanol und 45 ml 0,5 %i-ge Salzsäure in Anwesenheit von 1,0 g 10 ?6igen Pd/Kohle-Katalysator 4 Stunden bei 5O0C und Normaldruck hydriert. Das noch warme Gemisch wird filtriert, der Katalysator mit heißem Wasser nachgewaschen, die vereinigten Filtrate in Vakuum auf ein Drittel des ursprünglichen Volumens eingedampft, abgekühlt, und das auskristallisierte 1-Hydrazinophthalazin.Hydrochlorid abgesaugt un^ b«l 1050C getrocknet. Die Ausbeute beträgt 6,9 g(91 0A), Schmp. 272-275°C(Zers.)«The resulting product is charcoal catalyst in 120 ml of methanol and 45 ml 0.5% i-ge hydrochloric acid in the presence of 1.0 g of 10? 6igen Pd / 4 hours at 5O 0 C and atmospheric pressure. The still warm mixture is filtered, the catalyst is washed with hot water, the combined filtrates are evaporated to a third of the original volume in vacuo and cooled, and the 1-hydrazinophthalazine hydrochloride which has crystallized out is filtered off with suction and dried at 105 ° C. The yield is 6.9 g (91 0 A), melting point 272-275 ° C (decomp.) «
5,9 g (20 m Mol) i-Hydrazino-4-chlor-phthalazin werden in 65 ml Methanol und 20 ml 0,5 %ige Salzsäure in Anwesenheit von 0,5 g 10 ^igen Palladium/Kohle-Katalysator bei 200C und 1 atm 7 Stunden hydriert. Nach Aufarbeitung wie im Beispiel 1 werden 3»3 g. 1-Hydrazino-phthalazin.Hydrochlorid, Schmp. 271-2740C, erhalten.5.9 g (20 m mol) of i-hydrazino-4-chlorophthalazine are dissolved in 65 ml of methanol and 20 ml of 0.5 % strength hydrochloric acid in the presence of 0.5 g of 10 ^ strength palladium / carbon catalyst at 20 ° C and 1 atm hydrogenated for 7 hours. After working up as in Example 1, 3 »3 g. 1-hydrazino-phthalazin.Hydrochlorid, mp. 271-274 0 C is obtained.
Das 1-Hydrazino-A— chlor-phthalazin wird wie im Beispiel 2 bei einer Temperatur von 800C und einem Wasserstoffdruck von 15 atm eine halbe Stunde hydriert. Die Ausbeute an 1-Hydrazinophthala.zin. Hydrochloric! beträgt 3,5 g (90 % d.Th.), Schmp. 272-2750C.The 1-hydrazino-A- chloro-phthalazine as in Example 2 atm at a temperature of 80 0 C and a hydrogen pressure of 15 half an hour hydrogenated. The yield of 1-hydrazinophthala.zin. Hydrochloric! is 3.5 g (90% of theory). 272-275 0 C. m.p.
309885/1391309885/1391
5i9 S i-Hydrazino-4-chlor-phthalazin werden wie im Beispiel 3 in 85 ml 70 ^igen Methanol in Anwesenheit von 0,5 6 5 %igen Pd/BaSO^ Katalysator 2 Stunden hydriert.5i9 Si-hydrazino-4-chlorophthalazine are as in Example 3 in 85 ml of 70% methanol in the presence of 0.5 6 5% Pd / BaSO ^ catalyst hydrogenated for 2 hours.
Die Ausbeute beträgt 5,3 g (85 % d.Th.), Schiap. 0 The yield is 5.3 g (85 % of theory), Schiap. 0
309085/1391309085/1391
Claims (5)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
YU188372A YU34793B (en) | 1972-07-20 | 1972-07-20 | Process for preparing 1-hydrazino-phthalazine hydrochloride |
Publications (1)
Publication Number | Publication Date |
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DE2311510A1 true DE2311510A1 (en) | 1974-01-31 |
Family
ID=25555981
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19732311510 Pending DE2311510A1 (en) | 1972-07-20 | 1973-03-08 | PROCESS FOR THE PREPARATION OF 1-HYDRAZINO-PHTHALAZINE.HYDROCHLORIDE |
Country Status (7)
Country | Link |
---|---|
AT (1) | AT321924B (en) |
CA (1) | CA992082A (en) |
CH (1) | CH575399A5 (en) |
DE (1) | DE2311510A1 (en) |
FR (1) | FR2193824B3 (en) |
GB (1) | GB1412684A (en) |
YU (1) | YU34793B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3277626A (en) * | 1963-10-17 | 1966-10-11 | Dur O Wal National Inc | Double shank adjustable wall tie |
-
1972
- 1972-07-20 YU YU188372A patent/YU34793B/en unknown
-
1973
- 1973-03-05 AT AT190473A patent/AT321924B/en not_active IP Right Cessation
- 1973-03-06 CH CH326173A patent/CH575399A5/xx not_active IP Right Cessation
- 1973-03-08 DE DE19732311510 patent/DE2311510A1/en active Pending
- 1973-03-09 GB GB1164473A patent/GB1412684A/en not_active Expired
- 1973-03-21 CA CA166,640A patent/CA992082A/en not_active Expired
- 1973-05-09 FR FR7316644A patent/FR2193824B3/fr not_active Expired
Also Published As
Publication number | Publication date |
---|---|
YU188372A (en) | 1979-09-10 |
CA992082A (en) | 1976-06-29 |
FR2193824B3 (en) | 1976-04-23 |
FR2193824A1 (en) | 1974-02-22 |
CH575399A5 (en) | 1976-05-14 |
YU34793B (en) | 1980-03-15 |
GB1412684A (en) | 1975-11-05 |
AT321924B (en) | 1975-04-25 |
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