DE1795849B2 - Process for the preparation of 2-benzimidazole-carbamic acid methyl ester - Google Patents
Process for the preparation of 2-benzimidazole-carbamic acid methyl esterInfo
- Publication number
- DE1795849B2 DE1795849B2 DE19671795849 DE1795849A DE1795849B2 DE 1795849 B2 DE1795849 B2 DE 1795849B2 DE 19671795849 DE19671795849 DE 19671795849 DE 1795849 A DE1795849 A DE 1795849A DE 1795849 B2 DE1795849 B2 DE 1795849B2
- Authority
- DE
- Germany
- Prior art keywords
- benzimidazole
- carbamic acid
- methyl ester
- preparation
- acid
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 6
- TWFZGCMQGLPBSX-UHFFFAOYSA-N carbendazim Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 3
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 4
- -1 alkyl chloroformate Chemical compound 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 3
- ZSYJMXLJNPEAGP-UHFFFAOYSA-N methyl n-cyanocarbamate Chemical compound COC(=O)NC#N ZSYJMXLJNPEAGP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OETHQSJEHLVLGH-UHFFFAOYSA-N metformin hydrochloride Chemical compound Cl.CN(C)C(=N)N=C(N)N OETHQSJEHLVLGH-UHFFFAOYSA-N 0.000 description 1
- SDDKIZNHOCEXTF-UHFFFAOYSA-N methyl carbamimidothioate Chemical class CSC(N)=N SDDKIZNHOCEXTF-UHFFFAOYSA-N 0.000 description 1
- NNBBQNFHCVVQHZ-UHFFFAOYSA-N methyl carbamimidothioate;sulfuric acid Chemical compound CSC(N)=N.OS(O)(=O)=O NNBBQNFHCVVQHZ-UHFFFAOYSA-N 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 150000004987 o-phenylenediamines Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles 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 in position 2
- C07D235/30—Nitrogen atoms not forming part of a nitro radical
- C07D235/32—Benzimidazole-2-carbamic acids, unsubstituted or substituted; Esters thereof; Thio-analogues thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
IlIl
CH3O-C-NH-CN
mit o-Phenylei'.diamin der Formel
NH,CH 3 OC-NH-CN
with o-Phenylei'.diamin of the formula
NH,
NH2 NH 2
dadurch gekennzeichnet, daß man die Umsetzung in Gegenwart von Wasser bei einem pH-Wert des Reaktionsmediums von 2,5 bis 4,5 und einer Temperatur von 40 bis 130° C vornimmt.characterized in that the reaction in the presence of water at a pH of the reaction medium of 2.5 to 4.5 and a temperature of 40 to 130 ° C undertakes.
ring.ring.
Der 2-Benzimidazol-carbaminsäuremethylester ist ein gutes Fungicid.The 2-benzimidazole-carbamic acid methyl ester is a good fungicide.
In der US-Patentschrift 30 10 968 ist ein Verfahren zur Herstellung von 2-Benzimidazol-carbaminsäurealkylestern beschrieben, wobei Thioharnstoff mit Dimethylsulfat zu 2-Methyl-thiopseudoharnstoffsulfat umgesetzt wird. Dieses Reaktionsprodukt wird dann mit einem Alkylchlorformiat und einer Base zu einem acylierten 2-Methyl-thiopseudoharnstoff umgesetzt, welcher dann weiter mit einem o-Phenylendiamin in Gegenwart einer protonischen Säure zu dem gewünschten Produkt umgesetzt wird. Dieses Verfahren hat den Nachteil, daß ein verhältnismäßig kostspieliges Material, nämlich Thioharnstoff, eingesetzt werden muß und daß Methylmercaptan entsteht.In US Pat. No. 3,010,968 there is a process for the preparation of 2-benzimidazole-carbamic acid alkyl esters described, whereby thiourea reacted with dimethyl sulfate to form 2-methyl-thiopseudourea sulfate will. This reaction product then becomes one with an alkyl chloroformate and a base acylated 2-methyl-thiopseudourea reacted, which then further with an o-phenylenediamine in The presence of a protonic acid is converted to the desired product. This procedure has the Disadvantage that a relatively expensive material, namely thiourea, must be used and that methyl mercaptan is formed.
Es ist weiterhin aus den bekanntgemachten Unterlagen des belgischen Patents 6 66 795 bekannt, 2-Benzimidazol-carbaminsäurealkylester dadurch herzustellen, daß man Alkylchlorformiate mit Cyanamid zu einem Alkylcyancarbamat und dieses Produkt mit einer o-Phenylendiaminverbindung umsetzt. Diese Reaktionen werden in organischen Lösungsmitteln, zweckmäßig Pyridin, durchgeführt. Die erhaltenen Ausbeuten an 2-Benzimidazol-carbaminsäurealkylester sind sehr ge-Das erfindungsgemäße Verfahren ist im Patentanspruch definiert.It is also known from the published documents of the Belgian patent 6 66 795, 2-benzimidazole-carbamic acid alkyl ester to produce by alkyl chloroformates with cyanamide to form an alkyl cyanocarbamate and this product with a converts o-phenylenediamine compound. These reactions are expedient in organic solvents Pyridine. The yields of 2-benzimidazole-carbamic acid alkyl ester obtained are very good The method according to the invention is defined in the claim.
Um den Ringschluß durchzuführen, muß der pH-Wert dui ch Zugabe der notwendigen Säure zwischen 2,5 und 4,5 gehalten werden. Hierzu kann man eine beliebige Säure verwenden, beispielsweise Ameisensäure, Essigsäure, Chlorwasserstoffsäure, Schwefelsäure, Phosphorsäure, Hydroxyessigsäure oder Sulfaminsäure. Das o-Phenylendliamin kann wahlweise in Form eines Mineralsäuresalzes oder als wäßrige Lösung zugegeben werden. Wenn o-Phenylendiaminsalze verwendet werden, ist die zur Erzielung des gewünschten pH-Wertes erforderliche Säuremenge entsprechend kleiner.To carry out the ring closure, the pH dui ch addition of the necessary acid must be between 2.5 and 4.5 are held. Any acid can be used for this, for example formic acid, acetic acid, Hydrochloric acid, sulfuric acid, phosphoric acid, hydroxyacetic acid or sulfamic acid. That o-Phenylenediamine can optionally be in the form of a Mineral acid salt or as an aqueous solution are added. If o-phenylenediamine salts are used, the amount of acid required to achieve the desired pH value is correspondingly smaller.
Die Reaktion tritt bei Temperaturen oberhalb 40° C ein; vorzugsweise wird während der Umsetzung erhitzt, um die Reaktion beschleunigt zu Ende zu führen. Die Wärmezufuhr ist deshalb wichtig, weil die Reaktion bei niedrigen Temperaturen zu langsam sein würde. Das Reaktionsgemisch sollte vorzugsweise im Temperaturbereich von 60 bis 105° C gehalten werden. Die Reaktion kann auch, wenn dies gewünscht ist, unter Druck durchgeführt werden. Wenn dies geschieht, kann die Temperatur bis auf 130° C steigen.The reaction occurs at temperatures above 40 ° C; heating is preferably carried out during the reaction, in order to accelerate the reaction to completion. The supply of heat is important because the reaction takes place low temperatures would be too slow. The reaction mixture should preferably be in the temperature range from 60 to 105 ° C. If desired, the reaction can also be carried out under pressure be performed. When this happens, the temperature can rise to 130 ° C.
Während des Erhitzens fällt das gewünschte Produkt aus. Die Beendigung des Ausfallens ist somit ein Anzeichen dafür, daß das Reaktionsgemisch ausreichend lange erhitzt worden ist, um die Reaktion zu Ende zu führen. Die Zeitdauer ist nicht kritisch und hängt von der Temperatur und dem pH-Wert ab. So kann die Reaktionsdauer bei einer Temperatur zwischen 70 und 105° C 5 bis 30 Minuten betragen. Wenn niedrigere Temperaturen angewandt werden, ist die Reaktionsdauer länger.During the heating, the desired product precipitates. The cessation of failure is thus a Evidence that the reaction mixture has been heated long enough to complete the reaction respectively. The length of time is not critical and depends on the temperature and the pH. So can the The reaction time at a temperature between 70 and 105 ° C. is 5 to 30 minutes. If lower Temperatures are applied, the reaction time is longer.
Das gewünschte Produkt kann dann nach irgendeiner der herkömmlichen Methoden, beispielsweise durch Sprühtrocknung, Filtration oder Zentrifugierung, gewonnen werden, oder es kann durch Destillation des Wassers in irgendein anderes flüssiges Medium übergeführt werden.The desired product can then be obtained by any of the conventional methods, for example by Spray drying, filtration or centrifugation, or it can be obtained by distillation of the Water can be transferred to any other liquid medium.
In der Reaktion können die Reaktanten in den in der nachfolgenden Tabelle angezeigten Moläquivalent-Verhältnissen verwendet werden:In the reaction, the reactants can be used in the molar equivalent ratios shown in the table below be used:
ReaktantenReactants
Moläquivalente BevorzugteMolar Equivalents Preferred
MoläquivalenteMole equivalents
Methyleyancarbamat 1 bis 3 1 bis 1,8Methyl yan carbamate 1 to 3 1 to 1.8
o-Phtnylendiamin 1 1o-Phtnylenediamine 1 1
oder Derivate davonor derivatives thereof
Es versteht sich, daß die molaren Konzentrationen an der oberen Grenze nicht kritisch sind; jedoch ist das Verfahren bei den höheren Konzentrationen unzweckmäßig oder unwirtschaftlich.It will be understood that the molar concentrations at the upper limit are not critical; however that is Process inexpedient or uneconomical at the higher concentrations.
Das als Ausgangssubstanz dienende Methylcyancar- ·. bamat kann gemäß den nachfolgenden Gleichungen hergestellt werden: The methylcyancar- · serving as the starting substance. bamat can be made according to the following equations:
CNCN
Il pH 6-13 IIl pH 6-13 I.
+ mCI —C-OCH3 — * MC1« + M(N-CO2CH3),,+ mCI —C-OCH 3 - * MC1 "+ M (N-CO 2 CH 3 ) ,,
H + H +
NH(CN)-CO2CH3 NH (CN) -CO 2 CH 3
CNCN
Il pH 6-13 IIl pH 6-13 I.
mH2NCN + mCl-C — OCHj + 2M(OH)n, ; > M(N-CO2CH3),,, + MCIn, + 2mH2OmH 2 NCN + m Cl-C - OCHj + 2M (OH) n,; > M (N-CO 2 CH 3 ) ,,, + MCI n , + 2 m H 2 O
H2OH 2 O
Hierbei bedeutenHere mean
M ein Alkalimetall oder ein Erdalkalimetall und /η die Wertigkeit von M,M is an alkali metal or an alkaline earth metal and / η is the valence of M,
H+ kann von irgendeiner Säure herstammen.H + can come from any acid.
Man gibt 49,5 Teile o-Phenylendiamin, 140 Teile Wasser und 54 Teile Methylcyancarbamat in einen Rundkolben, der mit Beschickungsöffnungen, Rührer, Rückflußkühler und Meßkopf für den pH-Wert ausgerüstet ist. Man erhitzt das Reaktionsgemiüch auf 95°C und hält 1 Stunde und 15 Minuten bei 95 bis 97°C. Während dieser Zeit hält man den pH-Wert des Reaktionsgemisches durch Zugabe von konzentrierter Salzsäure bei 3,8 bis 4,2. Man kühlt das Reaktionsgemisch auf 20°C, filtriert das feste Produkt ab, wäscht dieses mit Wasser und Aceton und trocknet es in der Luft. Man erhält so 80,3 Teile 2-Benzimidazol-carbaminsäuremeihylester; F. 310-3200C (Zersetzung); Ausbeute: 93%, bezogen auf o-Phenylendiamin. v, 49.5 parts of o-phenylenediamine, 140 parts of water and 54 parts of methyl cyanocarbamate are added to a round-bottom flask equipped with charging openings, stirrer, reflux condenser and measuring head for the pH. The reaction mixture is heated to 95.degree. C. and kept at 95 to 97.degree. C. for 1 hour and 15 minutes. During this time, the pH of the reaction mixture is kept at 3.8 to 4.2 by adding concentrated hydrochloric acid. The reaction mixture is cooled to 20 ° C., the solid product is filtered off, washed with water and acetone and dried in the air. 80.3 parts of 2-benzimidazole-carbamic acid methyl ester are obtained in this way; F. 310-320 0 C (decomposition); Yield: 93% based on o-phenylenediamine. v,
H + H +
NH(CN)-CO2CH3 NH (CN) -CO 2 CH 3
Das eingesetzte Methylcyancarbamat erhält man wie folgt:The methyl cyanocarbamate used is obtained as follows:
In einen 1-1-Kolben, welcher mit einem Rührer und einem Thermometer ausgerüstet ist, gibt man 90,4 Teile einer 47°/oigen Cyanamidlösung zusammen mit 122 Teilen Wasser. Man rührt diese Lösung und gibt allmählich und gleichzeitig 97,5 Teile Methylchlorformiat und 169 Teile einer 50%igen Natriumhydroxidlösung hinzu. Man hält die Temperatur bei 45 bis 50° C und den pH-Wert des Gemisches bei 6,8 bis 7,2 während der Zugabe. Die erhaltene Lösung säuert man mit 83 Teilen konzentrierter Salzsäure auf einen pH-Wert von 1 an und kühlt auf 20°C. Dann extrahiert man die Lösung 6mal mit 125 Teilen Methylenchlorid. Man trocknet die vereinigten Methylenchloridlösungeri über 35 Teilen wasserfreiem Natriumsulfat und konzentriert die Lösung. Das erhaltene hellgelbe öl besteht aus 84,59 Teilen Methylcyancarbamat. Man titriert 0,5913 Teile dieser Verbindung mit 55,2 Teilen 0,1 N-Natriumhydroxidlösung gegen Phenolphthalein. Dies ergibt eine Reinheit von 93,3% und eine Ausbeute von 79%, bezogen auf Cyanamid. Der Brechungsindex dieser Verbindung ist 1,439834.In a 1-1 flask equipped with a stirrer and If a thermometer is fitted, 90.4 parts of a 47% cyanamide solution are added together with 122 Share water. This solution is stirred and 97.5 parts of methyl chloroformate are gradually added simultaneously and 169 parts of a 50% sodium hydroxide solution. The temperature is kept at 45 to 50 ° C and the pH of the mixture at 6.8 to 7.2 during the addition. The solution obtained is acidified with 83 parts concentrated hydrochloric acid to a pH value of 1 and cool to 20 ° C. Then the solution is extracted 6 times with 125 parts of methylene chloride. You dry them combined methylene chloride solution over 35 parts of anhydrous sodium sulfate and concentrated the Solution. The pale yellow oil obtained consists of 84.59 parts of methyl cyanocarbamate. 0.5913 parts are titrated this compound with 55.2 parts of 0.1 N sodium hydroxide solution against phenolphthalein. This gives a Purity of 93.3% and a yield of 79% based on cyanamide. The refractive index of this Connection is 1.439834.
Claims (1)
ΗC-N-COOCH 3
Η
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59438466A | 1966-11-15 | 1966-11-15 | |
| US67473967A | 1967-10-12 | 1967-10-12 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1795849A1 DE1795849A1 (en) | 1977-02-24 |
| DE1795849B2 true DE1795849B2 (en) | 1978-06-29 |
| DE1795849C3 DE1795849C3 (en) | 1979-03-01 |
Family
ID=27081960
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1967P0043394 Granted DE1668557B2 (en) | 1966-11-15 | 1967-11-14 | PROCESS FOR MANUFACTURING 2-BENZIMIDAZOLE CARBAMIC ACID METHYLESTER |
| DE19671795849 Expired DE1795849C3 (en) | 1966-11-15 | 1967-11-14 | Process for the preparation of 2-benzimidazole-carbamic acid methyl ester |
| DE19671793733 Pending DE1793733A1 (en) | 1966-11-15 | 1967-11-14 | ALKYLCYANIC CARBAMATE SALT WITH O-PHENYLENEDIAMINES, PROCESS FOR THEIR PREPARATION AND AGENTS CONTAINING SUCH COMPOUNDS |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1967P0043394 Granted DE1668557B2 (en) | 1966-11-15 | 1967-11-14 | PROCESS FOR MANUFACTURING 2-BENZIMIDAZOLE CARBAMIC ACID METHYLESTER |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19671793733 Pending DE1793733A1 (en) | 1966-11-15 | 1967-11-14 | ALKYLCYANIC CARBAMATE SALT WITH O-PHENYLENEDIAMINES, PROCESS FOR THEIR PREPARATION AND AGENTS CONTAINING SUCH COMPOUNDS |
Country Status (16)
| Country | Link |
|---|---|
| AT (2) | AT286311B (en) |
| BE (1) | BE706519A (en) |
| BR (1) | BR6794666D0 (en) |
| CH (1) | CH547291A (en) |
| DE (3) | DE1668557B2 (en) |
| DK (2) | DK132078C (en) |
| DO (1) | DOP1967001423A (en) |
| ES (1) | ES347053A1 (en) |
| FI (1) | FI48736C (en) |
| GB (1) | GB1185237A (en) |
| IL (1) | IL28858A (en) |
| LU (1) | LU54805A1 (en) |
| NL (1) | NL6715433A (en) |
| NO (1) | NO123460B (en) |
| SE (1) | SE342227B (en) |
| YU (1) | YU33788B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2227919C2 (en) * | 1972-06-08 | 1982-12-23 | Bayer Ag, 5090 Leverkusen | Process for the preparation of benzimidazol-2-yl-carbamic acid methyl ester |
| DE3323024A1 (en) * | 1983-06-25 | 1985-01-03 | Hoechst Ag, 6230 Frankfurt | METHOD FOR REDUCING BY-PRODUCT SHARES IN THE PRODUCTION OF CARBENDAZIM |
-
1967
- 1967-10-30 IL IL2885867A patent/IL28858A/en unknown
- 1967-11-07 LU LU54805D patent/LU54805A1/xx unknown
- 1967-11-08 CH CH547291D patent/CH547291A/en not_active IP Right Cessation
- 1967-11-09 AT AT1007667A patent/AT286311B/en not_active IP Right Cessation
- 1967-11-09 DO DO1967001423A patent/DOP1967001423A/en unknown
- 1967-11-09 AT AT735570A patent/AT296330B/en not_active IP Right Cessation
- 1967-11-10 SE SE1543667A patent/SE342227B/xx unknown
- 1967-11-11 ES ES347053A patent/ES347053A1/en not_active Expired
- 1967-11-13 BR BR19466667A patent/BR6794666D0/en unknown
- 1967-11-14 FI FI306567A patent/FI48736C/en active
- 1967-11-14 BE BE706519D patent/BE706519A/xx not_active IP Right Cessation
- 1967-11-14 DE DE1967P0043394 patent/DE1668557B2/en active Granted
- 1967-11-14 NL NL6715433A patent/NL6715433A/xx unknown
- 1967-11-14 DE DE19671795849 patent/DE1795849C3/en not_active Expired
- 1967-11-14 DE DE19671793733 patent/DE1793733A1/en active Pending
- 1967-11-14 NO NO17051867A patent/NO123460B/no unknown
- 1967-11-14 DK DK568667A patent/DK132078C/en active
- 1967-11-14 GB GB5177967A patent/GB1185237A/en not_active Expired
- 1967-11-15 YU YU222767A patent/YU33788B/en unknown
-
1968
- 1968-10-29 DK DK523968A patent/DK120286B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| YU222767A (en) | 1977-10-31 |
| DOP1967001423A (en) | 1972-12-13 |
| NO123460B (en) | 1971-11-22 |
| DK132078B (en) | 1975-10-20 |
| BR6794666D0 (en) | 1973-05-15 |
| NL6715433A (en) | 1968-05-16 |
| DE1795849C3 (en) | 1979-03-01 |
| SE342227B (en) | 1972-01-31 |
| AT296330B (en) | 1972-02-10 |
| DK120286B (en) | 1971-05-10 |
| AT286311B (en) | 1970-12-10 |
| DE1795849A1 (en) | 1977-02-24 |
| LU54805A1 (en) | 1968-01-31 |
| DK132078C (en) | 1976-03-15 |
| DE1793733A1 (en) | 1973-03-01 |
| IL28858A (en) | 1971-08-25 |
| BE706519A (en) | 1968-03-18 |
| DE1668557A1 (en) | 1971-01-21 |
| DE1668557B2 (en) | 1977-04-28 |
| YU33788B (en) | 1978-05-15 |
| CH547291A (en) | 1974-03-29 |
| FI48736C (en) | 1974-12-10 |
| GB1185237A (en) | 1970-03-25 |
| FI48736B (en) | 1974-09-02 |
| ES347053A1 (en) | 1969-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1795849C3 (en) | Process for the preparation of 2-benzimidazole-carbamic acid methyl ester | |
| EP0057889B1 (en) | Process for preparing 1-alkyl-2-chloro-5-nitro-benzene-4-sulphonic acids | |
| DE1668557C3 (en) | Process for the preparation of 2-benzimidazole-carbamic acid methyl ester | |
| US2275378A (en) | Polyalkylene ether disulphonyl halides and a process of making them | |
| DE2658961B2 (en) | Process for the preparation of 1-hydroxy-3-aminopropane-l, l-diphosphonic acids | |
| DE834992C (en) | Process for the preparation of N-alkyl or N-aralkyl derivatives of oxazolidine-2, 4-dynes | |
| CH626071A5 (en) | Process for preparing 3-phenyl-6-pyridazone | |
| DE2143709A1 (en) | ||
| DE1670283A1 (en) | Process for the preparation of hexahydropyrimidine derivatives | |
| DE2415748A1 (en) | PROCESS FOR PRODUCING POLYHALOGENATED NICOTIC ACIDS | |
| DE2819798A1 (en) | PROCESS FOR PRODUCING 3-PHENYL-PYRIDAZONE- (6) | |
| DE1912954C3 (en) | Process for the preparation of benzoxazolone-6-ßhydroxyäthylsulfon | |
| DE2203461C3 (en) | Process for the preparation of halogen-substituted 3-hydroxybenzo [c] -cinnoline derivatives | |
| DE855566C (en) | Process for the production of pentamethylenetetramine sulfone | |
| DE2256614A1 (en) | PROCESS FOR THE PREPARATION OF 2- (2AMINOBENZOYL) PYRIDINES | |
| DE1493910A1 (en) | Process for the preparation of nitriliotriacetonitrile | |
| DE1947948C3 (en) | Process for the preparation of sulfanilamido-I ^ .S-thiadiazole derivatives | |
| DE1952086C3 (en) | Process for the preparation of 6-nitro-9-amino-2-ethoxyacridine | |
| DE1443913C (en) | Process for the preparation of N cyanoiminocarbonic acid ester amides | |
| DE1543806C (en) | Process for the production of asparagine derivatives | |
| AT227696B (en) | Process for the preparation of 2-amino-oxazoles | |
| CH539649A (en) | Antibacterial sulphanilamido-1,2,5-thiadea- - zole prodn from 4-substd 3-chloro 1,2,5-thia- | |
| DE3243980A1 (en) | METHOD FOR PRODUCING GUANYL UREA SULFAMATE | |
| DE1793615B (en) | Process for the preparation of 3-aryl-7-amino-coumarins. Eliminated from: 1768665 | |
| DE2801152A1 (en) | PROCESS FOR THE PREPARATION OF N,N'-DIMETHYL-4,4'-DIPYRIDYLIUM DIHALOGENIDE BY QUARTERNATION OF DIPYRIDYL DIACETATE |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) |