DE2400415C3 - Process for the preparation of 3-aminopyrazoles - Google Patents

Process for the preparation of 3-aminopyrazoles

Info

Publication number
DE2400415C3
DE2400415C3 DE19742400415 DE2400415A DE2400415C3 DE 2400415 C3 DE2400415 C3 DE 2400415C3 DE 19742400415 DE19742400415 DE 19742400415 DE 2400415 A DE2400415 A DE 2400415A DE 2400415 C3 DE2400415 C3 DE 2400415C3
Authority
DE
Germany
Prior art keywords
general formula
aminopyrazoles
preparation
carbon atoms
compounds
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.)
Expired
Application number
DE19742400415
Other languages
German (de)
Other versions
DE2400415A1 (en
DE2400415B2 (en
Inventor
Guenter Prof. Dr. 6900 Heidelberg Ege
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.)
BASF SE
Original Assignee
BASF SE
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.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to DE19742400415 priority Critical patent/DE2400415C3/en
Priority to US532756A priority patent/US3920693A/en
Priority to CH1737574A priority patent/CH599162A5/xx
Priority to FR7500021A priority patent/FR2256917B1/fr
Priority to GB204/75A priority patent/GB1486731A/en
Priority to IT47527/75A priority patent/IT1026236B/en
Priority to JP50000139A priority patent/JPS5096567A/ja
Publication of DE2400415A1 publication Critical patent/DE2400415A1/en
Publication of DE2400415B2 publication Critical patent/DE2400415B2/en
Application granted granted Critical
Publication of DE2400415C3 publication Critical patent/DE2400415C3/en
Expired legal-status Critical Current

Links

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
    • C07D231/10—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
    • C07D231/14—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/38—Nitrogen atoms

Description

in derin the

R Wasserstoff oder gegebenenfalls substituiertes Alkyl, Cycloalkyl, Aralkyl oder Phenyl undR is hydrogen or optionally substituted alkyl, cycloalkyl, aralkyl or phenyl and

R1 Wasserstoff oder Alkyl, Cycloalkyl, Aralkyl oder gegebenenfalls substituiertes Phenyl bedeuten,R 1 denotes hydrogen or alkyl, cycloalkyl, aralkyl or optionally substituted phenyl,

dadurch gekennzeichnet, daß man Verbindungen der allgemeinen Formelcharacterized in that one compounds of the general formula

1515th

2020th

R1—CH = C-CNR 1 -CH = C-CN

I
χI.
χ

2525th

in der X Chlor oder Brom bedeutet, im alkalischen jo Medium mit Hydrazinen der allgemeinen Formelin which X is chlorine or bromine, in alkaline jo Medium with hydrazines of the general formula

R-NH-NH2 R-NH-NH 2

umsetzt, wobei R und R1 die angegebenen Bedeutungen aufweisen.converts, where R and R 1 have the meanings given.

J5J5

4040

Die Erfindung betrifft ein Verfahren zur Herstellung von 3-Aminopyrazolen der allgemeinen Formel IThe invention relates to a process for the preparation of 3-aminopyrazoles of the general formula I

4545

(D(D

in derin the

R Wasserstoff oder gegebenenfalls substituiertes Alkyl,Cycloalkyl, Aralkyl oder Phenyl und 55R is hydrogen or optionally substituted Alkyl, cycloalkyl, aralkyl or phenyl and 55

R1 Wasserstoff oder Alkyl, Cycloalkyl, Aralkyl oder gegebenenfalls substituiertes Phenyl bedeuten,R 1 denotes hydrogen or alkyl, cycloalkyl, aralkyl or optionally substituted phenyl,

das dadurch gekennzeichnet ist, daß man Verbindungen der allgemeinen Formel Ilwhich is characterized in that compounds of the general formula II

6060

R1—CH = C-CNR 1 -CH = C-CN

I
χI.
χ

(II)(II)

65 R-NH-NH2 65 R-NH-NH 2

(UI)(UI)

in der X Chlor oder Brom bedeutet, im alkalischenin which X is chlorine or bromine, in the alkaline

umsetzt, wobei R und R' die angegebenen Bedeutungen aufweisen.converts, where R and R 'have the meanings given exhibit.

Reste R sind beispielsweise Alkyl mit 1 bis 4 C-Atomen, Hydroxyalkyl mit 2 oder 3 C-Atomen, Cyanalkyl mit 2 oder 3 C-Atomen, Carbamoylalkyl mit 2 oder 3 C-Atomen, Cyclohexyl oder Benzyl und insbesondere Wasserstoff.R radicals are, for example, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms, Cyanoalkyl with 2 or 3 carbon atoms, carbamoylalkyl with 2 or 3 carbon atoms, cyclohexyl or benzyl and especially hydrogen.

Im einzelnen seien neben den bereits genannten für R aufgeführt:In addition to those already mentioned for R, the following are listed in detail:

Methyl, Äthyl, Propyl, Butyl, /J-Hydroxyäthyl oder -propyl, 0-Cyanäthyl, /J-Cyan-0-methyläthyl oder 0-CarbamoyläthyI.Methyl, ethyl, propyl, butyl, / I-hydroxyethyl or -propyl, 0-cyanoethyl, / I-cyano-0-methylethyl or O-carbamoyl ethyl I.

Die Reste R" sind z. B. Methyl,Cyclohexyl. Phenyl und insbesondere Wasserstoff.The radicals R ″ are, for example, methyl, cyclohexyl, phenyl and especially hydrogen.

Zweckmäßigerweise führt man die Umsetzung der Verbindungen der allgemeinen Formel I! mit denen der allgemeinen Formel III so durch, daß man die Verbindungen der allgemeinen Formel III in alkalischer Lösung oder Suspension vorlegt und eine Verbindung der allgemeinen Formel II allmählich zugibt Zu Beginn der Reaktion ist es dabei zweckmäßig, zu kühlen.The reaction of the compounds of the general formula I is expediently carried out! with those of general formula III so that the compounds of general formula III in alkaline Introduce a solution or suspension and gradually add a compound of the general formula II at the beginning it is advisable to cool the reaction.

Zur Einstellung des alkalischen Bereichs eignen sich z. B. die üblichen Alkalien, wie NaOH, KOH, Na2CO3, K2CO3, NaHCO3, KHCO3, NaOAlkyl (1 bis 4 C-Atome) oder Ca(OH)2; ferner sind tertiäre Amine oder ein Überschuß der Verbindungen der allgemeinen Formel III brauchbar. Einzelheiten der Herstellung sind dem Beispiel zu entnehmen.To adjust the alkaline range, z. B. the usual alkalis, such as NaOH, KOH, Na 2 CO 3 , K 2 CO 3 , NaHCO 3 , KHCO 3 , NaOalkyl (1 to 4 carbon atoms) or Ca (OH) 2 ; tertiary amines or an excess of the compounds of the general formula III can also be used. Details of the production can be found in the example.

Besonders wertvoll ist das neue Verfahren zur Herstellung des unsubstituierten 3(5)-Aminopyrazols.The new process for the preparation of the unsubstituted 3 (5) -aminopyrazole is particularly valuable.

Gegenüber den bisherigen Verfahren ([1] H. Reimlinger, A. van Overstraeten und H. G. Viehe.Chem.Ber.94,1036(1961),[2]H. DomundA. Z u b e k, Org. Synth. 48, 8 (1968) und [3] K. J. Klebe und C. L H abraken. Synthesis 1973, 294) zur Herstellung von 3(5)-Aminopyrazolen bietet das neue Verfahren große Vorteile in der Einfachheit der Durchführung und der Anzahl der notwendigen Operationen, da es im Eintopf durchgeführt werden kann. Man erhält die Pyrazole in vorzüglicher Ausbeute und hoher Reinheit.Compared to the previous process ([1] H. Reimlinger, A. van Overstraeten and H. G. Viehe.Chem.Ber.94,1036 (1961), [2] H. DomundA. Z u b e k, Org.Synth. 48, 8 (1968) and [3] K. J. Klebe and C. L H abraken. Synthesis 1973, 294) for The new process offers great advantages in the simplicity of the production of 3 (5) -aminopyrazoles Carrying out and the number of operations necessary, since it can be carried out in a stew can. The pyrazoles are obtained in excellent yield and high purity.

Die Pyrazole der allgemeinen Formel I sind wertvolle Diazokomponenten, z. B. zur Herstellung basischer Farbstoffe.The pyrazoles of the general formula I are valuable diazo components, e.g. B. for the production of basic Dyes.

Beispiel 1example 1

Zu einer Lösung von 140 g (1 Mol) K2CO3 in 400 ml Wasser gibt man 55 g (1,1 Mol) Hydrazinhydrat und tropft unter starkem Rühren bei 5 bis 10° C (Eis-Kochsalz-Kühlung) 87,5 g (1 Mol) 2-ChioracryInitril unter Stickstoff innerhalb von 1 Stunde hinzu. Man rührt eine Stunde bei Raumtemperatur, 1,5 Stunden bei 40 bis 500C und läßt über Nacht stehen. Dann extrahiert man 24 Stunden mit Essigester und destilliert das zurückbleibende rohe öl (75 g, 90%) im Hochvakuum unter Stickstoff. Man erhält 58 g (70%) 3(5)-Aminopyrazol vom Kp. 120 bis 122° C bei 04 Torr. Die Verbindung wird beim Kühlen, besser beim Animpfen fest und hat den Fp. -36° C. Übereinstimmend im IR-Spektrum mit authentischem 3(5)-Aminopyrazol · Pikrat: Fp.=55 g (1.1 mol) of hydrazine hydrate are added to a solution of 140 g (1 mol) of K 2 CO 3 in 400 ml of water and 87.5 are added dropwise with vigorous stirring at 5 to 10 ° C. (ice-salt cooling) g (1 mol) of 2-chloroacrylonitrile are added under nitrogen over the course of 1 hour. The mixture is stirred for one hour at room temperature, 1.5 hours at 40 to 50 ° C. and left to stand overnight. It is then extracted for 24 hours with ethyl acetate and the crude oil that remains (75 g, 90%) is distilled in a high vacuum under nitrogen. 58 g (70%) 3 (5) -aminopyrazole with a boiling point of 120 ° to 122 ° C. at 04 Torr are obtained. The compound solidifies on cooling, or better on inoculation, and has a melting point of -36 ° C. Corresponding in the IR spectrum with authentic 3 (5) -aminopyrazole · picrate: melting point =

2080C aus Methanol.208 0 C from methanol.

Analog der angegebenen Arbeitsweisen erhält man auch die in der folgenden Tabelle durch Angabe von R und R1 gekennzeichneten Aminopyrazole:The aminopyrazoles identified in the following table by specifying R and R 1 are also obtained analogously to the procedures given:

R1 R 1

R-]R-]

Bei
spielat
game RR. R1 R 1 22 CH3 CH 3 HH 33 CH2C6H5 CH 2 C 6 H 5 HH 44th C2H5 C 2 H 5 HH 55 C4H9 C 4 H 9 HH 66th CH2CH2OHCH 2 CH 2 OH HH 77th CH2CH2CNCH 2 CH 2 CN HH 88th CH2CH2CONH2 CH 2 CH 2 CONH 2 HH 99 CH2CHOHCH3 CH 2 CHOHCH 3 HH

2424 0000 415415 RR. -CH
\-CH
\ Bei
spielat
game CH3 CH 3 AusbeuleBulge 55 IOIO

IOIO

1111th

CH3 CH 3

CNCN

1212th HH .5 13.5 13 HH 1414th CH3 CH 3 67,7%
57:3%67.7%
57 : 3% 15
16
20
1715th
16
20th
17th CH2C6H5
QH5
CH3 CH 2 C 6 H 5
QH 5
CH 3 1818th CH2CH2CNCH 2 CH 2 CN 1919th C6H5CHCH3 C 6 H 5 CHCH 3

Ausbeuteyield

23,7%23.7%

70,7%70.7%

CH3 CH 3 64%64% C6H5 C 6 H 5 91%91% CH3 CH 3 59%59% CH3 CH 3 27%27% HH 25,7%25.7% C6H5 C 6 H 5 95%95% CH3 CH 3 50%50% HH 79,2%79.2%

Claims (1)

Patentanspruch:Claim: Verfahren zur Herstellung von 3-Aminopyrazolen der allgemeinen Formel 5 Process for the preparation of 3-aminopyrazoles of the general formula 5 Medium mit Hydrazinen der allgemeinen Formel HlMedium with hydrazines of the general formula Hl R-NR-N NH,NH, ίοίο
DE19742400415 1974-01-05 1974-01-05 Process for the preparation of 3-aminopyrazoles Expired DE2400415C3 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
DE19742400415 DE2400415C3 (en) 1974-01-05 1974-01-05 Process for the preparation of 3-aminopyrazoles
US532756A US3920693A (en) 1974-01-05 1974-12-16 Production of 3-aminopyrazoles
CH1737574A CH599162A5 (en) 1974-01-05 1974-12-30
FR7500021A FR2256917B1 (en) 1974-01-05 1975-01-02
GB204/75A GB1486731A (en) 1974-01-05 1975-01-03 Production of 3-aminopyrazoles
IT47527/75A IT1026236B (en) 1974-01-05 1975-01-03 PROCEDURE FOR THE PRODUCTION OF 3 AMMINOPIRAZOLS
JP50000139A JPS5096567A (en) 1974-01-05 1975-01-06

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19742400415 DE2400415C3 (en) 1974-01-05 1974-01-05 Process for the preparation of 3-aminopyrazoles

Publications (3)

Publication Number Publication Date
DE2400415A1 DE2400415A1 (en) 1975-07-17
DE2400415B2 DE2400415B2 (en) 1978-05-24
DE2400415C3 true DE2400415C3 (en) 1979-01-18

Family

ID=5904196

Family Applications (1)

Application Number Title Priority Date Filing Date
DE19742400415 Expired DE2400415C3 (en) 1974-01-05 1974-01-05 Process for the preparation of 3-aminopyrazoles

Country Status (1)

Country Link
DE (1) DE2400415C3 (en)

Also Published As

Publication number Publication date
DE2400415A1 (en) 1975-07-17
DE2400415B2 (en) 1978-05-24

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