DE1155773B - Process for the preparation of acylhydrazones - Google Patents
Process for the preparation of acylhydrazonesInfo
- Publication number
- DE1155773B DE1155773B DEF35469A DEF0035469A DE1155773B DE 1155773 B DE1155773 B DE 1155773B DE F35469 A DEF35469 A DE F35469A DE F0035469 A DEF0035469 A DE F0035469A DE 1155773 B DE1155773 B DE 1155773B
- Authority
- DE
- Germany
- Prior art keywords
- chloride
- bromo
- acetylhydrazide
- pyridinium
- acylhydrazones
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Pyridine Compounds (AREA)
Description
DEUTSCHESGERMAN
PATENTARiTPATENTARY
kl. 12 ο 22 kl. 12 ο 22
INTERNATIONALE KL.INTERNATIONAL KL.
C07c;dC07c; d
F35469IVb/12oF35469IVb / 12o
BEKANNTMACHUNG
DER ANMELDUNG
UNDAUSGABEDER
AUSLEGESCHRIFT: 17. OKTOBER 1963 NOTICE
THE REGISTRATION
ANDOUTPUTE
EDITORIAL: OCTOBER 17, 1963
Es ist bereits bekannt, daß in bestimmter Weise kernsubstituierte x-Halogen-zimtaldehyde bakteriostatische und fungistatische Eigenschaften besitzen (vgl. The Indian Journal of Pharmacy, 14 [1952], S. 3 bis 5, und 18 [1956], S. 396 bis 401, sowie deutsche Auslegeschrift 1 103 318). Die geringe Wasserlöslichkeit dieser bekannten Verbindungen bedingt jedoch die Verwendung von Lösungsvermittlern.It is already known that in a certain way nucleus-substituted x-halo-cinnamaldehydes are bacteriostatic and have fungistatic properties (cf. The Indian Journal of Pharmacy, 14 [1952], Pp. 3 to 5, and 18 [1956], pp. 396 to 401, as well as German Auslegeschrift 1 103 318). The low water solubility However, these known compounds require the use of solubilizers.
Es wurde gefunden, daß man Acylhydrazone mit guten Ausbeuten erhält, wenn man x-Brom-zimtaldehyde der allgemeinen FormelIt has been found that acylhydrazones are obtained in good yields if x-bromo-cinnamaldehydes are used the general formula
Verfahren zur Herstellung
von AcylhydrazonenMethod of manufacture
of acylhydrazones
-CH = C-CHO-CH = C-CHO
BrBr
worin R für Chlor, Brom, die Nitrogruppe oder die Cyangruppe steht, in alkoholischen Lösungsmitteln und in Gegenwart von Säuren mit Trimethylammonium-acetylhydrazidchlorid oder Pyridinium-acetylhydrazidchlorid zur Umsetzung bringt, und daß die so erhaltenen Verfahrenserzeugnisse eine wesentlich bessere biologische Wirkung entfalten und eine 100-bis 200mal größere Wasserlöslichkeit besitzen als die vorerwähnten bekannten entsprechenden Aldehyde. Das Verfahren gemäß der Erfindung wird in alkoholischen Lösungsmitteln durchgeführt, wobei als solche vorteilhaft aliphatische Alkohole mit 1 bis 4 Kohlenstoffatomen verwendet werden. Man arbeitet ferner in Gegenwart von Säuren, von denen beispielsweise Halogenwasserstoffsäuren wie Salzsäure oder Schwefelsäure bzw. organische Säuren wie Essigsäure oder Ameisensäure verwendet werden. Die Umsetzung wird zweckmäßig in der Weise durchgeführt, daß die als Ausgangsstoffe verwendeten Λ-Brom-zimtaldehyde Anmelder:where R stands for chlorine, bromine, the nitro group or the cyano group, in alcoholic solvents and in the presence of acids with trimethylammonium acetylhydrazide chloride or pyridinium acetylhydrazide chloride to the reaction, and that the process products thus obtained are an essential develop better biological effects and have 100 to 200 times greater water solubility than the aforementioned known corresponding aldehydes. The method according to the invention is carried out in alcoholic Solvents carried out, as such advantageously aliphatic alcohols with 1 to 4 carbon atoms are used. You also work in the presence of acids, of which, for example Hydrogen halide acids such as hydrochloric acid or sulfuric acid or organic acids such as acetic acid or formic acid can be used. The reaction is expediently carried out in such a way that the Λ-bromocinnamaldehyde used as starting materials Applicant:
Farbwerke Hoechst AktiengesellschaftFarbwerke Hoechst Aktiengesellschaft
vormals Meister Lucius & Brüning,formerly Master Lucius & Brüning,
Frankfurt/M.Frankfurt / M.
Dr. Hans Wissmann, Frankfurt/M.-Unterliederbach, und Dr. Walter Siedel, Bad Soden (Taunus),Dr. Hans Wissmann, Frankfurt / M.-Unterliederbach, and Dr. Walter Siedel, Bad Soden (Taunus),
sind als Erfinder genannt wordenhave been named as inventors
in alkoholischer Lösung vorgelegt und nach Zusatz der Säuren ebenfalls in alkoholischer Lösung mit einer Suspension von Trimethylammoniurn-acetylhydrazidchlorid bzw. Pyridinium-acetylhydrazidchlorid versetzt werden. Die Reaktion selbst wird vorteilhaft bei mäßig erhöhter Temperatur, insbesondere bei der Siedetemperatur des verwendeten Lösungsmittels, vorgenommen. Im allgemeinen fallen die gewünschten Verfahrenserzeugnisse aus der alkoholischen Reaktionslösung in kristallisierter Form aus. Sollte infolge zu hoher Löslichkeit der Verfahrensprodukte eine derartige Kristallisierung nicht sofort erfolgen, so kann auch eine Ausfällung mit beispielsweise Diäthyläther vorgenommen werden.presented in alcoholic solution and after adding the acids also in alcoholic solution with a Suspension of trimethylammonium acetylhydrazide chloride or pyridinium acetylhydrazide chloride are added will. The reaction itself becomes advantageous at a moderately elevated temperature, especially at the boiling point of the solvent used. In general, those that are desired fall Process products from the alcoholic reaction solution in crystallized form. Should as a result too high solubility of the process products such crystallization cannot take place immediately precipitation can also be carried out with, for example, diethyl ether.
Die Verfahrenserzeugnisse der Formel
RThe process products of the formula
R.
• — CH = C — CH = N — NH — CO — CH2- N(CH3)3 Br• - CH = C - CH = N - NH - CO - CH 2 - N (CH 3 ) 3 Br
' — CH = C — CH = N — NH — CO — CH2 — N'- CH = C - CH = N - NH - CO - CH 2 - N
BrBr
ClCl
+
Cl+
Cl
309 728/281309 728/281
worin R die angegebene Bedeutung besitzt, stellen hochwirksame Fungistatika dar, die sich gegenüber bekannten Verbindungen vergleichbarer chemischer Struktur durch erheblich bessere Wirksamkeit auszeichnen. In der Tabelle I werden einige der neuen Verfahrenserzeugnisse hinsichtlich ihrer Wirksamkeit gegen Hautpilze, Soor und Verrottungspilze mit einschlägigen bekannten Verbindungen verglichen, wobeiin which R has the meaning given, represent highly effective fungistats, which oppose each other known compounds of comparable chemical structure are characterized by significantly better effectiveness. Table I lists some of the new process products in terms of their effectiveness against skin fungi, thrush and rotting fungi compared with relevant known compounds, whereby
die angegebenen Zahlen Konzentrationen der verschiedenen geprüften Verbindungen in v/ml darstellen, die ausreichend waren, um bei einer Versuchsdauer von etwa 18 Tagen das Wachstum der im einzelnen aufgeführten Pilze auf festen Nährböden völlig zu verhindern. Aus diesen Angaben ist die überlegene Wirksamkeit der Verfahrenserzeugnisse klar ersichtlich. the figures given represent concentrations of the various compounds tested in v / ml, which were sufficient for the growth of the individual with a test duration of about 18 days to prevent the listed fungi on solid culture media completely. From this information is the superior one Effectiveness of the process products clearly evident.
sporon
gypseumMifcro
sporon
gypseum
Tricho-
phyton
rubrumHuh
Tricho-
phyton
rubrum
Tricho-
phyton
tonsurans;mushrooms
Tricho-
phyton
tonsurans
phyton
epilansTricho-
phyton
epilans
Candida
albicans
504S (
Candida
albicans
504
Candida
albicans
Y 12003or
Candida
albicans
Y 1200
Asper-
gillus
nigerRot
Asper
gillus
Niger
Tricho-
■ derma
viridefungi
Tricho-
■ derma
viride
nium-acetylhydrazidchlorid (vgl.
USA.-Patentschrift 2 670 348) ...5-chlorosalicylidene trimethylammo-
nium acetylhydrazide chloride (cf.
U.S. Patent 2,670,348) ...
tylhydrazidchlorid (vgl. USA.-
Patentschrift 2 670 348) 5-chlorosalizyliden-pyridinium-ace-
tylhydrazide chloride (see USA.-
Patent specification 2,670,348)
deutsche Auslegeschrift 1 103 318)a-bromo-p-cyano-cinnamaldehyde (cf.
German interpretation document 1 103 318)
Indian Journal of Pharmacy, 18
[1956], S. 396 «-Bromo-p-nitro-cinnamaldehyde (cf.
Indian Journal of Pharmacy, Jan.
[1956], p. 396
methylammonium-acetylhydrazid-
chlorid «-Bromo-p-chlorocinnamylidene-tri-
methylammonium acetylhydrazide
chloride
idinium-acetylhydrazidchlorid ...a-bromo-p-chlorocinnamylidene-pyr-
idinium acetylhydrazide chloride ...
idinium-acetylhydrazidchlorid ...a-bromo-p-cyancinnamylidene-pyr-
idinium acetylhydrazide chloride ...
Von besonderer Bedeutung ist auch die erheblich bessere Wasserlöslichkeit der neuen Verfahrenserzeugnisse gegenüber vergleichbaren bekannten Verbindungen, die deren Eignung als Zusätze zu Desinfektionsmitteln, Seifen, Spülmitteln usw. begründet. In der nachstehenden Tabelle II sind die Löslichkeiten einiger der neuen Verfahrenserzeugnisse in Wasser bei 200C den entsprechenden Löslichkeiten von vergleichbaren bekannten Verbindungen gegenübergestellt, soOf particular importance is the significantly better water solubility of the new process products compared to comparable known compounds, which explains their suitability as additives to disinfectants, soaps, detergents, etc. In Table II below, the solubilities of some of the new process products in water at 20 ° C. are compared with the corresponding solubilities of comparable known compounds, see above
Tabelle II (Fortsetzung)Table II (continued)
in Wasser
bei 20°Csolubility
in water
at 20 ° C
trimethylammonium-acetyl-
hydrazidchlorid «-Bromo-p-chlorocinnamylidene-
trimethylammonium acetyl
hydrazide chloride
pyridinium-acetylhydrazid-
chlorid a-bromo-p-chlorocinnamylidene-
pyridinium acetylhydrazide
chloride
in Wasser
bei 20° Csolubility
in water
at 20 ° C
7
86th
7th
8th
trimethylammonium-acetyl-
hydrazidchlorid
a-Brom-p-nitrocinnamyliden-
pyridinium-acetylhydrazid-
chlorid
«-Brom-p-cyancinnamyliden-
pyridinium-acetylhydrazid-
chlorid Λ-bromo-p-nitrocinnamylidene-
trimethylammonium acetyl
hydrazide chloride
a-bromo-p-nitrocinnamylidene-
pyridinium acetylhydrazide
chloride
«-Brom-p-cyancinnamyliden-
pyridinium acetylhydrazide
chloride
0,177%
0,119%0.22%
0.177%
0.119%
ac - Brom -A- nitrocinnamyliden - trimethylammoniumacetylhydrazidchlorid 6 g a-Brom-4-nitro-zimtaldehyd werden in 90 ml absolutem Methanol heiß gelöst. Der Lösung wird nach Zusatz von 0,3 ml lOnormaler methanolischer Salzsäure und unter Umschütteln eine Suspension von 4,5 g Trimethylammonium-acetylhydrazidchlorid (Girard-Reagenz T) in 10 ml Methanol zugesetzt. Nach 15minutigem Kochen unter Rückfluß wird das Reaktionsgemisch gekühlt, das ausgefallene a. - Brom - 4 - nitrocinnamyliden - trimethylammonium- ac - bromo -A- nitrocinnamylidene - trimethylammoniumacetylhydrazide chloride 6 g of a-bromo-4-nitro-cinnamaldehyde are dissolved in 90 ml of absolute methanol while hot. After adding 0.3 ml of 10 normal methanolic hydrochloric acid and shaking, a suspension of 4.5 g of trimethylammonium acetylhydrazide chloride (Girard reagent T) in 10 ml of methanol is added to the solution. After refluxing for 15 minutes, the reaction mixture is cooled and the precipitated a. - bromine - 4 - nitrocinnamylidene - trimethylammonium-
acetylhydrazidchlorid abfiltriert, mit absolutem Äther gewaschen und getrocknet. Die Ausbeute beträgt 6,35 g (63% der Theorie); Schmelzpunkt: 194 bis 195°C.Acetylhydrazide chloride was filtered off, washed with absolute ether and dried. The yield is 6.35 g (63% of theory); Melting point: 194 to 195 ° C.
In analoger Weise werden, ausgehend von Trimethylammonium-acetylhydrazid, erhalten:In an analogous manner, starting from trimethylammonium acetylhydrazide, the following are obtained:
nium-acetylhydrazidchlorid
«-Brom^-chlorcinnamyliden-trimethylammo-
nium-acetylhydrazidchlorid^ -Bromo-4-chlorocinnamylidene-trimethylammo-
nium acetyl hydrazide chloride
«-Bromo ^ -chlorcinnamylidene-trimethylammo-
nium acetyl hydrazide chloride
aldehyd
ac-Brom-2-chlor-zimt-
aldehyd«-Bromo-4-chloro-cinnamon-
aldehyde
ac-bromo-2-chloro-cinnamon
aldehyde
191 bis 192° C210 ° C
191 to 192 ° C
63 % der Theorie80% of theory
63% of theory
Beispiel 2 aldehyd und Pyridinium - acetylhydrazidchlorid, χ - Brom - 4 - nitrocinnamyliden - pyridinium - acetyl- κ . Brom - 4 - nitrocinnamyliden - pyridinium - acetylhydrazidchlorid hydrazidchlorid vom Schmelzpunkt 2530C (unter Entsprechend der im Beispiel 1 angegebenen Vor- 20 Zersetzung) erhalten. Die Ausbeute beträgt 50% schrift wird, ausgehend von «-Brom-4-nitro-zimt- der Theorie.Example 2 aldehyde and pyridinium - acetylhydrazide chloride, χ - bromine - 4 - nitrocinnamylidene - pyridinium - acetyl- κ . Bromo - 4 - nitrocinnamyliden - pyridinium - acetylhydrazidchlorid hydrazidchlorid (20 decomposition According to the advantages indicated in Example 1) of melting point 253 0 C. The yield is 50%, based on “-Bromo-4-nitro-cinnamon” theory.
Zersetzung)266 0 C (under
Decomposition)
acetylhydrazidchlorid«-Bromo ^ -chlorcinnamylidene-pyridinium-
acetyl hydrazide chloride
aldehyd-Bromo-4-chloro-cinnamon-
aldehyde
acetylhydrazidchlorid* -Bromo-2-chlorocinnamylidene-pyridinium-
acetyl hydrazide chloride
aldehyd«-Bromo-2-chloro-cinnamon-
aldehyde
hydrazidchloridS ^ -dibromo-cinnamylidene-pyridinium-acetyl-
hydrazide chloride
hydrazidchlorid«-Bromo-p-cyancinnamyliden-pyridinium-acetyl-
hydrazide chloride
aldehyd«-Brom-p-cyan-cinnamon-
aldehyde
Claims (1)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF35469A DE1155773B (en) | 1961-12-05 | 1961-12-05 | Process for the preparation of acylhydrazones |
GB4597962A GB1016654A (en) | 1961-12-05 | 1962-12-05 | New acyl-hydrazones,a process for preparing them,and preparations containing them |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF35469A DE1155773B (en) | 1961-12-05 | 1961-12-05 | Process for the preparation of acylhydrazones |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1155773B true DE1155773B (en) | 1963-10-17 |
Family
ID=7096013
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEF35469A Pending DE1155773B (en) | 1961-12-05 | 1961-12-05 | Process for the preparation of acylhydrazones |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE1155773B (en) |
GB (1) | GB1016654A (en) |
-
1961
- 1961-12-05 DE DEF35469A patent/DE1155773B/en active Pending
-
1962
- 1962-12-05 GB GB4597962A patent/GB1016654A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
GB1016654A (en) | 1966-01-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE2300325A1 (en) | PROCESS FOR THE PREPARATION OF (+) TRANS-CHRYSANTHEMIC ACID | |
DE1470017C3 (en) | Process for the preparation of 1,2-dihydroquinolines | |
DE1155773B (en) | Process for the preparation of acylhydrazones | |
DE2166270C3 (en) | Nicotinoylaminoethanesulfonyl-2amino-thiazole | |
EP0002802B1 (en) | Process for the preparation of halogenated anilines | |
DE1618207B2 (en) | PROCESS FOR THE PRODUCTION OF ALPHACHLORACETACETIC ACID MONOALKYLAMIDES | |
AT238161B (en) | Process for the preparation of new acylhydrazones | |
DE1912941B2 (en) | 1 -PhenyM-amino-e-methoxypridazinium salts | |
AT238164B (en) | Process for the preparation of new aldehydes and their acylhydrazones | |
DE1111163B (en) | Process for the preparation of mixtures from ª ‡, ª ‡, ª † - and ª ‡, ª †, ª † -trimethyladipic acid | |
DD210030A5 (en) | PROCESS FOR PRODUCING, IF NECESSARY, HALOGENATED ANILINE | |
DE2250106A1 (en) | PROCESS FOR THE PRODUCTION OF 1,1'DIANTHRAQUINONYLENE | |
DE1185605B (en) | Process for the preparation of acylhydrazones | |
DE1670967C3 (en) | 3-Imino-1,2-benzisothiazoline salts and process for their preparation | |
DE1158954B (en) | Process for the production of aldehydes | |
DE685321C (en) | Process for the production of quaternary nitrogen compounds | |
DE2153356A1 (en) | Process for the production of alpha amlinocarboxylic acids and their derivatives | |
AT225684B (en) | Process for the preparation of mixtures of α, α, γ- and α, γ, γ-trimethyladipic acid | |
DE1259871B (en) | Process for the preparation of N-chloroformylcarbamic acid esters | |
DE68697C (en) | Process for the preparation of basic disulfide compounds (thiurets) and salts thereof from alkyldithiobiurets | |
DE935667C (en) | Process for the preparation of phenanthridinium salts | |
DE1206422B (en) | Process for the preparation of 2,6-dichlorobenzonitrile | |
AT299244B (en) | Process for the production of new organotin compounds | |
DE2264638C2 (en) | 5'-acetyl-2,2'-cyclocytidine derivatives | |
DE494508C (en) | Process for the preparation of a condensation product from m-cresol and acetone |