DE1070635B - Process for the preparation of 1,5-unsubstituted 3-amino pymzenes - Google Patents
Process for the preparation of 1,5-unsubstituted 3-amino pymzenesInfo
- Publication number
- DE1070635B DE1070635B DENDAT1070635D DE1070635DA DE1070635B DE 1070635 B DE1070635 B DE 1070635B DE NDAT1070635 D DENDAT1070635 D DE NDAT1070635D DE 1070635D A DE1070635D A DE 1070635DA DE 1070635 B DE1070635 B DE 1070635B
- Authority
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- Germany
- Prior art keywords
- parts
- amino
- weight
- unsubstituted
- preparation
- 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 4
- 238000002360 preparation method Methods 0.000 title claims description 3
- 150000002429 hydrazines Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- KEVLRNAZDIXTTP-UHFFFAOYSA-N 2-cyano-3-oxopropanoic acid Chemical compound OC(=O)C(C=O)C#N KEVLRNAZDIXTTP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 2
- 125000004433 nitrogen atoms Chemical group N* 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- -1 3-amino-pyrazoles Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- JVVRJMXHNUAPHW-UHFFFAOYSA-N 1H-pyrazol-5-amine Chemical class NC=1C=CNN=1 JVVRJMXHNUAPHW-UHFFFAOYSA-N 0.000 description 4
- KGIWPGKKIFFMKP-UHFFFAOYSA-N 2-(ethoxymethylidene)-3-hydroxybutanedinitrile Chemical compound CCOC=C(C#N)C(O)C#N KGIWPGKKIFFMKP-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003217 pyrazoles Chemical class 0.000 description 4
- HKOOXMFOFWEVGF-UHFFFAOYSA-N Phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229940067157 phenylhydrazine Drugs 0.000 description 3
- KJAQRHMKLVGSCG-UHFFFAOYSA-N propan-2-ylhydrazine Chemical compound CC(C)NN KJAQRHMKLVGSCG-UHFFFAOYSA-N 0.000 description 3
- XXNOGQJZAOXWAQ-UHFFFAOYSA-N 4-chlorophenylhydrazine Chemical compound NNC1=CC=C(Cl)C=C1 XXNOGQJZAOXWAQ-UHFFFAOYSA-N 0.000 description 2
- HDZGCSFEDULWCS-UHFFFAOYSA-N Monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 150000002084 enol ethers Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- OEICGMPRFOJHKO-UHFFFAOYSA-N 2-(ethoxymethylidene)propanedinitrile Chemical compound CCOC=C(C#N)C#N OEICGMPRFOJHKO-UHFFFAOYSA-N 0.000 description 1
- GBHCABUWWQUMAJ-UHFFFAOYSA-N 2-hydrazinoethanol Chemical compound NNCCO GBHCABUWWQUMAJ-UHFFFAOYSA-N 0.000 description 1
- JXPDNDHCMMOJPC-UHFFFAOYSA-N 2-hydroxybutanedinitrile Chemical compound N#CC(O)CC#N JXPDNDHCMMOJPC-UHFFFAOYSA-N 0.000 description 1
- MZFBWODPTSTYAI-UHFFFAOYSA-N 5-amino-1-methylpyrazole-4-carbonitrile Chemical compound CN1N=CC(C#N)=C1N MZFBWODPTSTYAI-UHFFFAOYSA-N 0.000 description 1
- MAKQREKUUHPPIS-UHFFFAOYSA-N 5-amino-1-phenylpyrazole-4-carbonitrile Chemical compound NC1=C(C#N)C=NN1C1=CC=CC=C1 MAKQREKUUHPPIS-UHFFFAOYSA-N 0.000 description 1
- HWLUYAARRNLXJL-UHFFFAOYSA-N 5-amino-1-propan-2-ylpyrazole-4-carbonitrile Chemical compound CC(C)N1N=CC(C#N)=C1N HWLUYAARRNLXJL-UHFFFAOYSA-N 0.000 description 1
- FFNKBQRKZRMYCL-UHFFFAOYSA-N 5-amino-1H-pyrazole-4-carbonitrile Chemical compound NC1=NNC=C1C#N FFNKBQRKZRMYCL-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- KTMGNAIGXYODKQ-UHFFFAOYSA-N ethyl 2-cyano-3-ethoxyprop-2-enoate Chemical compound CCOC=C(C#N)C(=O)OCC KTMGNAIGXYODKQ-UHFFFAOYSA-N 0.000 description 1
- HQCMSFVKGNYGRP-UHFFFAOYSA-N ethyl 2-cyanoprop-2-eneperoxoate Chemical compound CCOOC(=O)C(=C)C#N HQCMSFVKGNYGRP-UHFFFAOYSA-N 0.000 description 1
- AYJIUOZKKTUKKD-UHFFFAOYSA-N ethyl 5-amino-1-phenylpyrazole-4-carboxylate Chemical compound NC1=C(C(=O)OCC)C=NN1C1=CC=CC=C1 AYJIUOZKKTUKKD-UHFFFAOYSA-N 0.000 description 1
- OFSRMXPYRMMISS-UHFFFAOYSA-N ethyl 5-amino-1-propan-2-ylpyrazole-4-carboxylate Chemical compound CCOC(=O)C=1C=NN(C(C)C)C=1N OFSRMXPYRMMISS-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07D231/10—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
8/018/01
IMEKNAT. KL. C 07 dIMEKNAT. KL. C 07 d
C14323IVb/12pC14323IVb / 12p
ANMEXDETAG: 31. J A N U A R 1957ANMEXD DATE: JANUARY 31, 1957
BEKANNTMACHUNG DER ANMELDUNG UND AUSGABE DER AUSLEGESCHRIFT:NOTICE THE REGISTRATION AND ISSUE OF THE EDITORIAL:
10. DEZEMBER 1959DECEMBER 10, 1959
Gegenstand der Erfindung ist ein neues Verfahren zur Herstellung von Pyrazolen. Es ist schon vorgeschlagen worden, ß-Oxo-carbonsäurenitrile mit Hydrazin (vgl. Chemische Berichte, 87 [1954], S. 1600 bis 1604) zu 3-Amino-pyrazolen umzusetzen. Es ist ferner bekannt, daß sich Aldehydgruppen bei Reaktionen von /?-Dicarbonylverbindungen mit Hydrazinen ähnlich wie Ketogruppen verhalten. Es war jedoch nicht vorauszusehen, wie sich α-Cyan-a-formyl-essigsäure, die ja drei reaktionsfähige Gruppen enthält, bei der Reaktion mit Hydrazinen verhalten würde. Es wurde nun gefunden, daß man zu neuen Pyrazolverbindungen, nämlich 3-Amino-pyrazolen, die in 4-Stellung eine freie oder funktionell abgewandelte Carboxylgruppe aufweisen und in 1- und 5-Stellung unsubstituiert sind, gelangt, wenn man a-Cyan-a-formylessigsäure, gegebenenfalls in Form ihrer funktionellen Säure- und/oder Aldehyd-derivate mit an den Stickstoffatomen mindestens 3 Wasserstoffatome aufweisenden Hydrazinen umsetzt.The invention is a new method for Manufacture of pyrazoles. It has already been proposed to combine ß-oxo-carboxylic acid nitriles with hydrazine (cf. Chemical reports, 87 [1954], pp. 1600 to 1604) to 3-amino-pyrazoles. It is also known that aldehyde groups are formed in reactions of /? - dicarbonyl compounds behave similarly to keto groups with hydrazines. However, it was impossible to predict how it would turn out α-cyano-a-formyl-acetic acid, the three reactive ones Contains groups that would behave in reaction with hydrazines. It has now been found that one can become new Pyrazole compounds, namely 3-amino-pyrazoles, which are free or functionally modified in the 4-position Have carboxyl groups and are unsubstituted in the 1- and 5-positions, if you get a-cyano-a-formyl acetic acid, optionally in the form of their functional acid and / or aldehyde derivatives with on the nitrogen atoms at least 3 hydrogen atoms containing hydrazines.
Funktionelle Säurederivate sind in erster Linie solche, die eine Oxo- oder Iminogruppe aufweisen, wie Ester, Amide-oder Amidine; ferner auch Nitrile. Funktionell?" Aldehydderivate sind vor allem Enoläther, Acetale oder Mercaptale. Man verwendet als Ausgangsstoffe vorzugsweise die Enoläther von α-Cyan-a-formyl-essigsäure oder ihren funktioneilen Säurederivaten, in erster Linie die Alkoxymethylen-cyanessigsäure-alkylester, wie den Äthoxymethylencyanessigsäure-äthylester, ferner auch die Alkoxymethylen-malonitrile, wie das Äthoxymethylen-malonitril. Acid functional derivatives are mainly those having an oxo or imino group, such as ester, amide or e-amidines; also nitriles. Functional? "Aldehyde derivatives are mainly enol ethers, acetals or mercaptals. The starting materials used are preferably the enol ethers of α-cyano-α-formyl acetic acid or its functional acid derivatives, primarily the alkoxymethylene cyanoacetic acid alkyl esters, such as the ethoxymethylene cyanoacetic acid ethyl ester , also the alkoxymethylene malonitrile, such as ethoxymethylene malonitrile.
■ Als Hydrazine kommen insbesondere Hydrazin, Monoalkyloder-Mono-(hydroxyalkyl)- und Monoaryl-hydrazine in Betracht, z. B. Methylhydrazin, ß-Hydroxyäthylhydrazin, Isopropylhydrazin, Phenylhydrazin, Halogenphenyl-hydrazine, wie p-Chlorophenyl-hydrazin, Alkylphenylhydr azine.■ Hydrazines, in particular, are hydrazine, monoalkyl or mono- (hydroxyalkyl) and monoaryl hydrazines into consideration, e.g. B. methylhydrazine, ß-hydroxyethylhydrazine, Isopropylhydrazine, phenylhydrazine, halophenylhydrazines, such as p-chlorophenylhydrazine, alkylphenylhydrazine azines.
Die Kondensation der α-Cyan-a-formyl-essigsäure oder ihrer Derivate mit den Hydrazinen zu den Pyrazolen verläuft unter milden Bedingungen, zum Teil bei Zimmertemperatur und exotherm. Man kann auch bei höherer Temperatur und in Anwesenheit von Kondensationsmitteln arbeiten, z. B. in Gegenwart von Säuren. Vorteilhaft setzt man in Anwesenheit eines Verdünnungsmittels, wie eines Alkohols, Toluol oder Chloroform um. Die Reaktion kann am Beispiel der Umsetzung von Äthoxymethylencyanessigester mit Hydrazin wie folgt illustriert werden:The condensation of α-cyano-α-formyl-acetic acid or its derivatives with the hydrazines to give the pyrazoles runs under mild conditions, partly at room temperature and exothermic. You can also use higher Working temperature and in the presence of condensing agents, e.g. B. in the presence of acids. Advantageous is reacted in the presence of a diluent such as an alcohol, toluene or chloroform. The reaction can be illustrated using the example of the reaction of ethoxymethylene cyaneacetic ester with hydrazine as follows:
Verfahren zur Herstellung von 1,5-unsubstituierten 3-Amino-pyrazolenProcess for the preparation of 1,5-unsubstituted 3-amino-pyrazoles
Anmelder:Applicant:
CIBA Aktiengesellschaft, Basel (Schweiz)CIBA Aktiengesellschaft, Basel (Switzerland)
Vertreter: Dipl.-Ing. E. Splanemann, Patentanwalt, Hamburg 36, Neuer Wall 10Representative: Dipl.-Ing. E. Splanemann, patent attorney, Hamburg 36, Neuer Wall 10
Beanspruchte Priorität:Claimed priority:
Schweiz vom 10. Februar, 7. April, 16. Juli,Switzerland from February 10, April 7, July 16,
28. September 1956 und 2. Januar 1957September 28, 1956 and January 2, 1957
Dr. Jean Druey, Riehen,Dr. Jean Druey, Riehen,
und Dr. Paul Schmidt, Therwil (Schweiz),and Dr. Paul Schmidt, Therwil (Switzerland),
sind als Erfinder genannt wordenhave been named as inventors
Die verfahrensgemäß gewonnenen neuen Pyrazole, d. h. 1,5-unsubstituierte 3-Aminö-pyrazole, die in 4-Stellung eine freie oder funktionell abgewandelte Carboxylgruppe tragen, sindThe new pyrazoles obtained according to the process, d. H. 1,5-unsubstituted 3-amino-pyrazoles in the 4-position carry a free or functionally modified carboxyl group
Die Erfindung wird in den nachfolgenden Beispielen beschrieben. Die Beziehung zwischen Gewichtsteilen und Volumteilen ist dieselbe wie zwischen Gramm und Kubikcentimeter. Die Temperaturen werden in Celsiusgraden angegeben..The invention is illustrated in the following examples described. The relationship between parts by weight and parts by volume is the same as that between grams and Cubic centimeter. The temperatures are given in degrees Celsius.
17 Gewichtsteile Äthoxymethylencyanessigsäureäthylester werden in 100 Volumteilen Äthylalkohol gelöst. Die Lösung wird dann langsam mit einer Lösung von 10,8 Gewichtsteilen Phenylhydrazin in 50 Volumteilen Äthylalkohol versetzt. Zur Vervollständigung der Reaktion wird während 2 Stunden zum Sieden erhitzt. Man dampft im Vakuum zur Trockne, wonach ein rötliches Öl zurückbleibt, das bei Zusatz von Benzol kristallisiert. Durch Umkristallisation aus Essigester unter Zusatz von Tierkohle erhält man 2-Phenyl-3-amino-4-carbäthoxypyrazol der Formel .17 parts by weight of ethyl ethoxymethylene cyaneacetate are dissolved in 100 parts by volume of ethyl alcohol. The solution is then slowly mixed with a solution of 10.8 parts by weight of phenylhydrazine in 50 parts by volume Ethyl alcohol added. To complete the reaction, the mixture is heated to boiling for 2 hours. Man evaporates to dryness in vacuo, after which a reddish oil remains, which crystallizes when benzene is added. Recrystallization from ethyl acetate with the addition of animal charcoal gives 2-phenyl-3-amino-4-carbethoxypyrazole the formula.
C9H=OOCC 9 H = OOC
C0H=OOC-C =CH 0 C H = C = CH-OOC
NC. OC2H5
NH9 NC. OC 2 H 5
NH 9
H2NH 2 N
.C9H15OOC -ΠΓ-- η.C 9 H 15 OOC -ΠΓ-- η
in weißen Kristallen vom F. 99 bis 101°; Ausbeute 92%.in white crystals with a melting point of 99 to 101 °; Yield 92%.
909 688/397909 688/397
I 070 635I 070 635
8,5 Gewichtsteile Äthoxymethylencyanessigester werden in 500 Volumteile Alkohol gebracht; die Lösung wird dann mit 2,5 Volumteilen Hydrazinhydrat versetzt μηά während 6 Stunden am Rückfluß gekocht. Man dampft im Vakuum zur -Trockne und kristallisiert aus wenig Wasser. S-Amino^-carbäthoxy-pyrazol der Formel8.5 parts by weight of ethoxymethylene cyanogen acetate are brought into 500 parts by volume of alcohol; the solution will be then added μηά with 2.5 parts by volume of hydrazine hydrate refluxed for 6 hours. It is evaporated to dryness in vacuo and crystallized from a little Water. S-Amino ^ -carbethoxy-pyrazole of the formula
'"CH5OOC-'"CH 5 OOC-
H2N-H 2 N-
wird so in einer Ausbeute von 87 °/0 in weißen Kristallen vom F. 102 bis 103° erhalten.is as / in a yield of 87 ° 0 in white crystals, mp 102-103 °.
24,4 Gewichtsteile Äthoxymethylenmalonsäure-dinitril werden in 250 Volumteüen Äthylalkohol gelöst. Die Lösung wird dann langsam mit 22 Gewichtsteüen Phenylhydrazin versetzt und während 10 Stunden zum Sieden erhitzt. Man läßferkalten, wonach ein kristallines Produkt ausfällt, von dem abgenutscht wird. Durch nochmalige Kristallisation aus Alkohol erhält man 2-Phenyl-3-amino-4-cyan-pyrazol der Formel24.4 parts by weight of ethoxymethylene malonic acid dinitrile are dissolved in 250 parts by volume of ethyl alcohol. The solution is then slowly added with 22 parts by weight of phenylhydrazine added and heated to boiling for 10 hours. It is allowed to cool, after which a crystalline product fails, which is sucked off. Another crystallization from alcohol gives 2-phenyl-3-amino-4-cyano-pyrazole the formula
Eine Lösung von 85 Gewichtsteilen Äthoxymethylencyanessjgsäure-äthylester in 500 Volumteüen Alkohol wird langsam \ mit. 71 Gewichtsteüen p-Chlor-phenylhydrazin versetzt. Nach beendigter Zugabe wird zur Vervollständigung der Reaktion noch während 2 Stunden zum Sieden erhitzt. Man läßt erkalten und nutscht dann von dem ausgefallenen Niederschlag ab. Durch Umkristallisation aus Alkohol wird 2-p-Chlorphenyl-3-arnino-4-carbäthoxy-pyrazol der FormelA solution of 85 parts by weight Äthoxymethylencyanessjgsäure acid ethyl ester in 500 Volumteüen alcohol with slow \. 71 parts by weight of p-chlorophenylhydrazine added. When the addition is complete, the mixture is heated to boiling for a further 2 hours to complete the reaction. It is allowed to cool and the precipitate which has separated out is then suction filtered. Recrystallization from alcohol gives 2-p-chlorophenyl-3-arnino-4-carbethoxy-pyrazole of the formula
CH1=OOCCH 1 = OOC
H9N-H 9 N-
erhalten ;obtain ;
in weißen Kristallen vom F. 145 bis 146° Ausbeute 80 °/0.in white crystals with a melting point of 145 to 146 °, yield 80 ° / 0 .
NC-T-NC-T-
H9N-H 9 N-
50,7 Gewichtsteile Äthoxymethylen-cyanessigester50.7 parts by weight of ethoxymethylene cyanoacetic ester
werden in 400 Volumteüen Äthylalkohol gelöst. Die Lösung wird dann langsam mit 33 Gewichtsteüen 70 %igem /3-Hydroxyäthylhydrazin versetzt und während 10 Stunden am Rückfluß gekocht. Hierauf dampft man im Vakuum zur Trockne ein und destilliert den Rückstand im Hochvakuum. Man erhält so bei einem Kp.0,1 mm are dissolved in 400 parts by volume of ethyl alcohol. The solution is then slowly admixed with 33 parts by weight of 70% strength / 3-hydroxyethylhydrazine and refluxed for 10 hours. It is then evaporated to dryness in vacuo and the residue is distilled in a high vacuum. With a bp 0.1 mm is obtained
185 bis 187° 2-(/3-Hydroxyäthyl)-3-amino-4-carbäthoxypyrazol der Formel185 to 187 ° 2 - (/ 3-hydroxyethyl) -3-amino-4-carbethoxypyrazole the formula
C2H5OOC-C 2 H 5 OOC-
in KristaUen vom F. 135 bis 137°; Ausbeute 85°/0.in crystals from 135 to 137 °; Yield 85 ° / 0 .
8,2 Gewichtsteile Isopropylhydrazin werden in eine Lösung von 16,9 Gewichtsteüen Äthoxymethylencyanessigester in 100 Volumteüen Alkohol gebracht und während 12 Stunden zum Sieden erhitzt. Man dampft dann im Vakuum zur Trockne ein und destilliert den Rückstand im Vakuum. 2-Isopropyl-3-amino-4-carbäthoxy-pyrazol der Formel8.2 parts by weight of isopropylhydrazine are dissolved in a solution of 16.9 parts by weight of ethoxymethylene cyanoacetate Brought in 100 parts by volume of alcohol and heated to boiling for 12 hours. Then you steam in a vacuum to dryness and the residue is distilled in a vacuum. 2-isopropyl-3-amino-4-carbethoxy-pyrazole the formula
H9NH 9 N
CH9 CH 9
-CH2-OH-CH 2 -OH
CH.OOC - π CH.OOC - π
H2N-H 2 N-
"N'"N '
in einer Ausbeute von 87 °/0. Es erstarrt beim Erkalten und schmilzt bei 77 bis 79°.in a yield of 87 ° / 0th It solidifies when it cools and melts at 77 to 79 °.
48,8 Gewichtsteile Äthoxymethylen-malonitril werden in 500 Volumteüen Äthylalkohol gelöst. Die Lösung wird langsam mit 44 Gewichtsteüen /J-Hydroxyäthylhydrazin versetzt und während 10 Stunden am Rückfluß gekocht. Dann wird im Vakuum eingedampft und der Rückstand48.8 parts by weight of ethoxymethylene malonitrile are dissolved in 500 parts by volume of ethyl alcohol. The solution will be slowly with 44 parts by weight / I-hydroxyethylhydrazine added and refluxed for 10 hours. It is then evaporated in vacuo and the residue
aus Äthylalkohol umkristallisiert. 2-(/?-Hydroxyäthyl) 3-amino-4-cyano-pyrazol der Formelrecrystallized from ethyl alcohol. 2 - (/? - hydroxyethyl) 3-amino-4-cyano-pyrazole of the formula
CHCH
CH,CH,
CH,CH,
NC-TNC-T
H9N-H 9 N-
geht bei 10 mm 164 bis 166° über und erstarrt kristallin in der Vorlage. Die so erhaltenen farblosen Kristalle schmelzen von 46 bis 48°; Ausbeute 95 %.passes from 164 to 166 ° at 10 mm and solidifies in crystalline form in the original. The colorless crystals thus obtained melting from 46 to 48 °; Yield 95%.
Eine Lösung von 48,8 Gewichtsteüen Äthoxymethylenmalonitril in 500 Volumteüen Alkohol wird mit 30 Gewichtsteüen Isopropylhydrazin versetzt. Man erhitzt dann während 10 Stunden zum Sieden, dampft im Vakuum zur Trockne ein und kristallisiert aus viel Isopropyläther. 2-Isopropyl-3-amino-4-cyano-pyrazol wird so in weißen KristaUen vom F. 94 bis 95° in einer Ausbeute von 82°/0 erhalten.A solution of 48.8 parts by weight of ethoxymethylene malonitrile in 500 parts by volume of alcohol is mixed with 30 parts by weight of isopropylhydrazine. The mixture is then heated to boiling for 10 hours, evaporated to dryness in vacuo and crystallized from a large amount of isopropyl ether. 2-Isopropyl-3-amino-4-cyano-pyrazole is obtained in this way in white crystals with a melting point of 94 ° to 95 ° in a yield of 82 ° / 0 .
CH9 CH 9
-CH2-OH-CH 2 -OH
wird so in KristaUen vom F. 156 bis 158° erhalten.is obtained in this way in crystals from a temperature of 156 to 158 °.
Eine Lösung von 40 g Äthoxymethylen-malonitril in 400 cm3 Äthanol wird mit 27 g Methylhydrazin versetzt.A solution of 40 g of ethoxymethylene malonitrile in 400 cm 3 of ethanol is mixed with 27 g of methylhydrazine.
Man erhitzt dann während 10 Stunden zum Sieden, läßt erkalten und nutscht von dem ausgefaUenen Produkte ab.The mixture is then heated to the boil for 10 hours, allowed to cool and the fouled product is filtered off with suction.
2-Methyl-3-amino-4-cyano-pyrazol wird so in weißen KristaUen vom F. 219 bis 220° in einei Ausbeute von 87% erhalten.2-Methyl-3-amino-4-cyano-pyrazole is thus obtained in white crystals from a melting point of 219 to 220 ° in a yield of 87% received.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1070635B true DE1070635B (en) | 1959-12-10 |
Family
ID=595497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1070635D Pending DE1070635B (en) | Process for the preparation of 1,5-unsubstituted 3-amino pymzenes |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1070635B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1904894A1 (en) | 1968-02-02 | 1970-01-15 | Wellcome Found | Process for the preparation of pyrazolo- (3,4-d) -pyrimidines |
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0
- DE DENDAT1070635D patent/DE1070635B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1904894A1 (en) | 1968-02-02 | 1970-01-15 | Wellcome Found | Process for the preparation of pyrazolo- (3,4-d) -pyrimidines |
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