DE2417142A1 - PROCESS FOR PREPARING 3-PYRROLIDINYL- (1) -PROPYL-DITHIOCARBAMIC ACID - Google Patents

PROCESS FOR PREPARING 3-PYRROLIDINYL- (1) -PROPYL-DITHIOCARBAMIC ACID

Info

Publication number
DE2417142A1
DE2417142A1 DE2417142A DE2417142A DE2417142A1 DE 2417142 A1 DE2417142 A1 DE 2417142A1 DE 2417142 A DE2417142 A DE 2417142A DE 2417142 A DE2417142 A DE 2417142A DE 2417142 A1 DE2417142 A1 DE 2417142A1
Authority
DE
Germany
Prior art keywords
propyl
pyrrolidinyl
dithiocarbamic acid
reaction
preparing
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.)
Withdrawn
Application number
DE2417142A
Other languages
German (de)
Inventor
Paul-Ernst Dr Frohberger
Klaus Dr Sasse
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.)
Bayer AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Priority to DE2417142A priority Critical patent/DE2417142A1/en
Priority to DK134075A priority patent/DK136472C/en
Priority to SU2116859A priority patent/SU520048A3/en
Priority to BE154770A priority patent/BE827187A/en
Priority to GB1294075A priority patent/GB1455683A/en
Priority to IE687/75A priority patent/IE40891B1/en
Priority to FR7509824A priority patent/FR2267320B1/fr
Priority to IL47009A priority patent/IL47009A/en
Priority to IT22082/75A priority patent/IT1049401B/en
Priority to CH437775A priority patent/CH597211A5/xx
Priority to DD185278A priority patent/DD119590A5/xx
Priority to NL7504119A priority patent/NL7504119A/en
Priority to LU72226A priority patent/LU72226A1/xx
Priority to PL1975179431A priority patent/PL93129B1/pl
Priority to CS2413A priority patent/CS177043B2/cs
Priority to RO7581928A priority patent/RO65068A/en
Priority to HU75BA00003242A priority patent/HU172754B/en
Publication of DE2417142A1 publication Critical patent/DE2417142A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pyrrole Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

Bayer Aktiengesellschaft " 8 2T'i 7T42 Bayer Aktiengesellschaft " 8 2 T'i 7T 42

Zentralbereich Patente. Marken und LizenzenCentral Patents Department. Trademarks and licenses

SIr/As fi09 Leverki;sen· BayerwerkSIr / As fi09 Leverki; s e n · Bayerwerk

Verfahren zur Herstellung der 3-Pyrrolidinyl-(i J-dithiocarbamidsäure Process for the preparation of 3-pyrrolidinyl- (i J-dithiocarbamic acid

Die vorliegende Anmeldung betrifft, ein speziello.3 chemisches Verfahren zur Herstellung der bekannten fungizid wirksamen 3-Pyrrolidinyl-(i)-propyl-dithiocarbamidsäure.The present application relates to a special chemical Process for the preparation of the known fungicidally active 3-pyrrolidinyl- (i) -propyl-dithiocarbamic acid.

Es ist bereits bekannt geworden, daß man die 3-Pyrrolidinyl-(1)-propyl-dithiocarbamidsäure herstellen kann, wenn man 1-(3-Aminopropyl)-pyrrolidin und Schwefelkohlenstoff in Benzol bei 250C umsetzt. Man erhält hierbei nach Literaturangaben (siehe U.S.-Patentschrift 2 971 884, daselbst Spalten 3/4, Beispiel 1) ein Präparat mit dem Schmelzpunkt 147-1490C, dessen Analyse jedoch keine befriedigenden Werte aufweist. Die Verbindung dürfte daher nicht in reiner Form vorgelegen haben und das Herstellungsverfahren somit ungeeignet sein.It has already been known that (1) propyl dithiocarbamic acid can produce the 3-pyrrolidinyl, when 1- (3-aminopropyl) pyrrolidine is reacted and carbon disulfide in benzene at 25 0 C. Is obtained in this case according to the literature (see U.S. Patent No. 2,971,884, there columns 3/4, Example 1) a preparation with the melting point 147-149 0 C, however, the analysis of which has satisfactory values. The compound should therefore not have been present in pure form and the manufacturing process should therefore be unsuitable.

Es wurde nun gefunden, daß man die bekannte 3-Pyrrolidinyl-(1 )■ propyl-dithiocarbamidsäure der FormelIt has now been found that the known 3-pyrrolidinyl- (1) ■ propyl-dithiocarbamic acid of the formula

N-CH0-Ch0-CH2-NH-C-SH bzw,N-CH 0 -Ch 0 -CH 2 -NH-C-SH or,

Le A 15 586 - 1 -Le A 15 586 - 1 -

509844/1039509844/1039

24Ί7Η224Ί7Η2

durch Reaktion von 1-(3-Araino-propyl)-pyrrolidin der Formelby reaction of 1- (3-araino-propyl) -pyrrolidine of the formula

mit Schwefelkohlenstoff in guter Ausbeute und Reinheit nur dann erhält, wenn man die Umsetzung in wäßrigem Medium im Temperaturbereich von -10 bis +5O0C durchführt.only obtained with carbon disulfide in good yield and purity when the reaction is performed to + in an aqueous medium in the temperature range of -10 5O 0 C.

Es ist als ausgesprochen überraschend zu bezeichnen, daß man durch die Stahl von Wasser als Lösungsmittel die 3-Pyrro-lidinyl-(i)-propyl-dithiocarbamidsäure in reiner Form mit einem Schmelzpunkt vom 175°C erhält. Das Verfahren stellt einen technischen Fortschritt dar, da nach dem literaturbekannten Verfahren die fragliche Verbindung (wie aus den in der U.S.Patentschrift 2 971 884 genannten Daten geschlossen werden muß) nicht in reiner Form erhalten werden konnte.It can be described as extremely surprising that the steel of water as a solvent, the 3-pyrrolidinyl- (i) -propyl-dithiocarbamic acid in pure form with one Melting point of 175 ° C is obtained. The process represents a technical advance, as it is known from the literature Process the compound in question (as deduced from the data cited in U.S. Patent 2,971,884 must) could not be obtained in pure form.

Die Umsetzung kann durch das folgende Formelschema wiedergegeben werden:The implementation can be represented by the following equation:

Ie A 15 586 -2-Ie A 15 586 -2-

509844/1039509844/1039

2Λ171422Λ17142

N-CH2-CH2-CH2-NH2+CS2 » I N-CH2-CH2-CH2-NH-O-SN-CH 2 -CH 2 -CH 2 -NH 2 + CS 2 >> I N-CH 2 -CH 2 -CH 2 -NH-OS

Die Ausgangsstoffe 1-(3-Aminopropyl)—pyrrolidin (vgl. hierzu Beilsteins Handbuch der organischen Chemie H 20, E II 6) und Schwefelkohlenstoff sind allgemein bekannte Verbindungen.The starting materials 1- (3-aminopropyl) pyrrolidine (cf. Beilstein's Handbook of Organic Chemistry H 20 , E II 6) and carbon disulfide are generally known compounds.

Als Verdünnungsmittel wird erfindungsgemäß V/asser verwendet, wobei die Menge des wassers nicht von großer Bedeutung für Ausbeute und Reinheit ist.According to the invention, V / water is used as the diluent, whereby the amount of water is not of great importance for the yield and purity.

Die Umsetzung wird bei Temperaturen von -10 bis +500C, vorzugsweise zwischen 0 und 30 C vorgenommen.The reaction is carried out at temperatures of -10 to +50 0 C, preferably between 0 and 30 C.

Zur Durchführung des Verfahrens werden die Reaktionspartner vorzugsweise im stöchiometrischen Verhältnis miteinander zur Reaktion gebracht, wobei die Reihenfolge, in der die Reaktanten aufeinander treffen, ohne wesentliche Bedeutung für den Reaktionsablauf ist.To carry out the process, the reactants are preferably in a stoichiometric ratio to one another Brought reaction, the order in which the reactants meet is of no essential importance for the Reaction sequence is.

Die Aufarbeitung erfolgt durch Absaugen des Reaktionsproduktes und Umlösen aus Wasser.Working up is carried out by suctioning off the reaction product and dissolving from water.

Die erfindungsgemäß erhältliche Verbindung besitzt nach Literaturangaben eine fungizide Wirkung; erwähnt wird z.B. eine Wirkung gegen Alternaria solani (U.S. Patentschrift 2 971 884, Spalten 7/8).According to the literature, the compound obtainable according to the invention has a fungicidal effect; mentions, for example, an activity against Alternaria solani (U.S. Patent 2,971,884, Columns 7/8).

Le A 15 586 - 5 - Le A 15 586 - 5 -

50984A/103950984A / 1039

2417H22417H2

HerstellungsbeispielManufacturing example

N-OH0-CH0-CH0-IiH-C-S " I 2. 2 rs. N-OH 0 -CH 0 -CH 0 -IiH-CS " I 2.2 rs.

Zur Lösung von 128 g.(i Mol) 1-(3-Amino-propyl)-pyrrolidin in 600 ml Wasser läßt man unter Kühlung bei einer Temperatur von 10 bis 15°C 76 g (1 Mol) Schwefelkohlenstoff zutropfen. Das Gemisch wird 1 Stunde bei Raumtemperatur nachgerührt, das Kristallisat abgesaugt, mit Eiswasser und Methanol gewaschen und getrocknet. Man erhält 194 g 3-Pyrrolidinyl-(i)-propyl-dithiocarbamidsäure vom Schmelzpunkt 1750C, das sind 95 i° der Theorie. Die Verbindung läßt sich aus Wasser umlösen, der Schmelzpunkt (175 C unter Zersetzung) ändert sich dabei nicht.To a solution of 128 g (1 mol) 1- (3-aminopropyl) pyrrolidine in 600 ml water, 76 g (1 mol) carbon disulfide are added dropwise with cooling at a temperature of 10 to 15 ° C. The mixture is stirred for 1 hour at room temperature, the crystals are filtered off with suction, washed with ice water and methanol and dried. Are obtained 194 g 3-pyrrolidinyl (i) propyl dithiocarbamic acid of melting point 175 0 C, or 95 ° i of theory. The compound can be dissolved in water, the melting point (175 C with decomposition) does not change.

Analyse: Ber.: N 13,7 1°\ S 31,35 i° Gef.: Hf 13,8 $; S 31,30 $>. Analysis: Calc .: N 13.7 1 ° \ S 31.35 i ° Found: Hf 13.8 $; S $ 31.30>.

Bei einem in Benzol als Verdünnungsmittel nach Literaturangaben (U.S.-Patentschrift 2 971 884, Beispiel 1) hergestellten Muster wurden im Infrarotspektrum Verunreinigungen bei 1350 und 1390 cm"1 festgestellt.In the case of a sample prepared in benzene as a diluent according to the literature (US Pat. No. 2,971,884, Example 1), impurities were found in the infrared spectrum at 1350 and 1390 cm " 1 .

Le A -15 586 - 4 -Le A -15 586 - 4 -

5098U/10395098U / 1039

Claims (2)

2417H22417H2 PatentansprücheClaims 1/. Verfahren zur Herstellung von 3-i)yrrolidinyl-(i )-propyldithiocarbamidsäure der Formel1/. Process for the preparation of 3-i ) yrrolidinyl- (i) -propyldithiocarbamic acid of the formula 3 Il3 Il IT-Ch2-CH2-GH2-NH-O-SH bzw,IT-Ch 2 -CH 2 -GH 2 -NH-O-SH or, I SI S "-CH9-CH0-CH9-NH-C-S ) ("-CH 9 -CH 0 -CH 9 -NH-CS) ( durch Reaktion von 1-(3-Amino-propyl)-pyrrolidin der Formelby reaction of 1- (3-amino-propyl) -pyrrolidine of the formula -CH2-CH2-CH2-NH2 -CH 2 -CH 2 -CH 2 -NH 2 mit Schwefelkohlenstoff, dadurch gekennzeichnet, daß man die Umsetzung in wäßrigem Medium im Temperaturbereich von -10 bis +5O0C durchführt."characterized with carbon disulfide, which comprises carrying out the reaction in an aqueous medium in the temperature range from -10 to + 5O 0 C. " 2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man die Umsetzung zwischen 0 und 300C durchführt.2. The method according to claim 1, characterized in that the reaction between 0 and 30 0 C is carried out. Le A 15 586 - 5 - Le A 15 586 - 5 - 509844/1039509844/1039
DE2417142A 1974-04-09 1974-04-09 PROCESS FOR PREPARING 3-PYRROLIDINYL- (1) -PROPYL-DITHIOCARBAMIC ACID Withdrawn DE2417142A1 (en)

Priority Applications (17)

Application Number Priority Date Filing Date Title
DE2417142A DE2417142A1 (en) 1974-04-09 1974-04-09 PROCESS FOR PREPARING 3-PYRROLIDINYL- (1) -PROPYL-DITHIOCARBAMIC ACID
DK134075A DK136472C (en) 1974-04-09 1975-03-26 PROCEDURE FOR THE PREPARATION OF 3-PYRROLIDINYL- (1) -PROPYL-DITHIOCARBAMIIC ACID
SU2116859A SU520048A3 (en) 1974-04-09 1975-03-26 The method of obtaining 3pyrrolidinyl-1-propyldithiocarbamic acid
BE154770A BE827187A (en) 1974-04-09 1975-03-26 PROCESS FOR THE PREPARATION OF 3-PYRROLIDINYL- (1) -PROPYL-DITHIOCARBAMIC ACID
GB1294075A GB1455683A (en) 1974-04-09 1975-03-27 Process for the preparation of 3-pyrrolidinyl-1-propyl-dithio carbamic acid
IE687/75A IE40891B1 (en) 1974-04-09 1975-03-27 Process for the preparation of 3-pyrrolidinyl-(1)-propyl-dithiocarbamic acid
FR7509824A FR2267320B1 (en) 1974-04-09 1975-03-28
IL47009A IL47009A (en) 1974-04-09 1975-04-04 Process for the preparation of 3-pyrrolidinyl-(1)-propyl-dithiocarbamic acid and fungicidal compositions containing it
IT22082/75A IT1049401B (en) 1974-04-09 1975-04-07 PROCESS FOR THE PRODUCTION OF PYROLIDINYL I ACID PROPILDITIO CARBAMMICO
CH437775A CH597211A5 (en) 1974-04-09 1975-04-07
DD185278A DD119590A5 (en) 1974-04-09 1975-04-07
NL7504119A NL7504119A (en) 1974-04-09 1975-04-07 METHOD FOR PREPARING 3-PYRROLIDINYL-1 PROPYL-DITHIOCARBAMIC ACID.
LU72226A LU72226A1 (en) 1974-04-09 1975-04-07
PL1975179431A PL93129B1 (en) 1974-04-09 1975-04-08
CS2413A CS177043B2 (en) 1974-04-09 1975-04-08
RO7581928A RO65068A (en) 1974-04-09 1975-04-08 PROCESS FOR THE PREPARATION OF 3-PYROLIDINIL-(1) -PROPYLEDITHIOCARBAMIC ACID
HU75BA00003242A HU172754B (en) 1974-04-09 1975-04-09 Process for producing 3-pyrrolidinyl-bracket-1-bracket closed-propyl-dithio-carnamic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2417142A DE2417142A1 (en) 1974-04-09 1974-04-09 PROCESS FOR PREPARING 3-PYRROLIDINYL- (1) -PROPYL-DITHIOCARBAMIC ACID

Publications (1)

Publication Number Publication Date
DE2417142A1 true DE2417142A1 (en) 1975-10-30

Family

ID=5912516

Family Applications (1)

Application Number Title Priority Date Filing Date
DE2417142A Withdrawn DE2417142A1 (en) 1974-04-09 1974-04-09 PROCESS FOR PREPARING 3-PYRROLIDINYL- (1) -PROPYL-DITHIOCARBAMIC ACID

Country Status (17)

Country Link
BE (1) BE827187A (en)
CH (1) CH597211A5 (en)
CS (1) CS177043B2 (en)
DD (1) DD119590A5 (en)
DE (1) DE2417142A1 (en)
DK (1) DK136472C (en)
FR (1) FR2267320B1 (en)
GB (1) GB1455683A (en)
HU (1) HU172754B (en)
IE (1) IE40891B1 (en)
IL (1) IL47009A (en)
IT (1) IT1049401B (en)
LU (1) LU72226A1 (en)
NL (1) NL7504119A (en)
PL (1) PL93129B1 (en)
RO (1) RO65068A (en)
SU (1) SU520048A3 (en)

Also Published As

Publication number Publication date
CS177043B2 (en) 1977-07-29
RO65068A (en) 1979-02-15
DK136472B (en) 1977-10-17
IE40891L (en) 1975-10-09
DK136472C (en) 1978-03-28
HU172754B (en) 1978-12-28
IL47009A (en) 1977-11-30
FR2267320A1 (en) 1975-11-07
DK134075A (en) 1975-10-10
GB1455683A (en) 1976-11-17
IT1049401B (en) 1981-01-20
IL47009A0 (en) 1975-06-25
IE40891B1 (en) 1979-09-12
PL93129B1 (en) 1977-05-30
FR2267320B1 (en) 1978-09-29
LU72226A1 (en) 1976-03-02
BE827187A (en) 1975-09-26
CH597211A5 (en) 1978-03-31
DD119590A5 (en) 1976-05-05
NL7504119A (en) 1975-10-13
SU520048A3 (en) 1976-06-30

Similar Documents

Publication Publication Date Title
DE2803259A1 (en) PROCESS FOR THE PRODUCTION OF FLUOROBENZENE
DE2826452A1 (en) METHOD FOR PRODUCING SUBSTITUTED GUANIDINES
DE2454950C2 (en) Process for the preparation of 2-aminobutan-1-ol and its acid addition salts
DE2417142A1 (en) PROCESS FOR PREPARING 3-PYRROLIDINYL- (1) -PROPYL-DITHIOCARBAMIC ACID
DE2166270C3 (en) Nicotinoylaminoethanesulfonyl-2amino-thiazole
DE2150399A1 (en) Alpha-oximinobenzyl cyanides - useful as pesticide inters
DE2558517A1 (en) 4-METHYLIMIDAZOLE-5-CARBONIC ACID ISOPROPYLESTER AND A NEW PROCESS FOR ITS PRODUCTION
DE2148597A1 (en) PERFLUORALKYLSULFIC ACIDS AND THE METHOD FOR THEIR PRODUCTION
DE2603508C2 (en) Process for the preparation of "Isothiocyanates
EP0043024B1 (en) Process for the preparation of 5-amino isoxazoles
DE3044904A1 (en) FLUORINATED ANTHRANILE ACID AND ANTHRANILE ACID NITRILE AND METHOD FOR THE PRODUCTION THEREOF
DE2651371A1 (en) QUATERNAERE AMMONIUM SALTS
DE1161560B (en) Process for the production of hematopoietic ferrocene derivatives
DE1292664B (en) 1, 2, 3, 5, 6-pentathiacycloheptane, process for its preparation and use
DE2413189C2 (en) Process for the preparation of benzohydroquinones
DE19732030B4 (en) Process for the preparation of chloromethanesulfonyl chloride
DE2261272C3 (en) Process for the preparation of diaminomaleic acid dinitrile
DE3235045C2 (en) Process for the preparation of sulfonyl isocyanates
AT232980B (en) Process for the preparation of alkali metal cyanide dithioformates and dialkali salts of 1,2-dicyano-1,2-dimercaptoethene
DE1953356A1 (en) Process for the preparation of N-alkyl-N- (trihalomethylthio) sulfamide acid chlorides
DE2611602A1 (en) Stable iodine complexes with amides ureas and lactams - useful in disinfectants as bactericides and fungicides
DE1121607B (en) Process for the production of impure and pure bis (tetrachloroethyl) disulfide
AT265308B (en) Process for the preparation of N-benzyl-N ', N "-dimethylguanidine or its acid addition salts
AT274843B (en) Process for the preparation of N-benzyl-N ', N "-dimethylguanidine and its acid addition salts
AT258957B (en) Process for the preparation of pyrazinyl thiophosphates

Legal Events

Date Code Title Description
8130 Withdrawal