DE975295C - Process for the preparation of fungicidal derivatives of trichloromethyl mercaptan - Google Patents
Process for the preparation of fungicidal derivatives of trichloromethyl mercaptanInfo
- Publication number
- DE975295C DE975295C DEF17281A DEF0017281A DE975295C DE 975295 C DE975295 C DE 975295C DE F17281 A DEF17281 A DE F17281A DE F0017281 A DEF0017281 A DE F0017281A DE 975295 C DE975295 C DE 975295C
- Authority
- DE
- Germany
- Prior art keywords
- sulfamide
- dimethyl
- chloride
- solution
- trichloromethylsulfen
- 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
Links
- 238000002360 preparation method Methods 0.000 title claims description 4
- 230000000855 fungicidal effect Effects 0.000 title claims description 3
- ILSVYQNRDXIWLK-UHFFFAOYSA-N trichloromethanethiol Chemical class SC(Cl)(Cl)Cl ILSVYQNRDXIWLK-UHFFFAOYSA-N 0.000 title claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 20
- -1 N-substituted sulfamide Chemical class 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000000243 solution Substances 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000003388 sodium compounds Chemical class 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 5
- 241000233622 Phytophthora infestans Species 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000417 fungicide Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000010626 work up procedure Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 206010061217 Infestation Diseases 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 230000003032 phytopathogenic effect Effects 0.000 description 2
- DLESVPKKZGWYEZ-UHFFFAOYSA-N (dimethylsulfamoylamino)methane;sodium Chemical compound [Na].CNS(=O)(=O)N(C)C DLESVPKKZGWYEZ-UHFFFAOYSA-N 0.000 description 1
- VRSAVYUPMFCOAL-UHFFFAOYSA-N 1-(dimethylsulfamoylamino)-4-methylcyclohexane Chemical compound CC1CCC(NS(=O)(=O)N(C)C)CC1 VRSAVYUPMFCOAL-UHFFFAOYSA-N 0.000 description 1
- CDSYNWHHHNSMGB-UHFFFAOYSA-N 1-(dimethylsulfamoylamino)naphthalene Chemical compound C1=CC=C2C(NS(=O)(=O)N(C)C)=CC=CC2=C1 CDSYNWHHHNSMGB-UHFFFAOYSA-N 0.000 description 1
- UZUHWNHTNULJAV-UHFFFAOYSA-N 4-chloro-N-(dimethylsulfamoyl)-N-(trichloromethylsulfanyl)aniline Chemical compound ClC(Cl)(Cl)SN(S(=O)(=O)N(C)C)C1=CC=C(C=C1)Cl UZUHWNHTNULJAV-UHFFFAOYSA-N 0.000 description 1
- 240000007087 Apium graveolens Species 0.000 description 1
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 description 1
- 235000010591 Appio Nutrition 0.000 description 1
- YLRCOVJLUZPCAI-UHFFFAOYSA-N CCC(C=CC=C1C)=C1N(SC(Cl)(Cl)Cl)S(N(C)C)(=O)=O Chemical compound CCC(C=CC=C1C)=C1N(SC(Cl)(Cl)Cl)S(N(C)C)(=O)=O YLRCOVJLUZPCAI-UHFFFAOYSA-N 0.000 description 1
- RZKSMGUOCGNDLU-UHFFFAOYSA-N ClC(Cl)(Cl)SN(S(=O)(=O)N(C)C)C1=C(C=C(C=C1)C)C Chemical compound ClC(Cl)(Cl)SN(S(=O)(=O)N(C)C)C1=C(C=C(C=C1)C)C RZKSMGUOCGNDLU-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- QCDQDISRALTLNQ-UHFFFAOYSA-N N,N-dimethyl-N'-phenylsulfamide Chemical compound CN(C)S(=O)(=O)NC1=CC=CC=C1 QCDQDISRALTLNQ-UHFFFAOYSA-N 0.000 description 1
- 241001281803 Plasmopara viticola Species 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- 241001597359 Septoria apiicola Species 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
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229950005348 benzylsulfamide Drugs 0.000 description 1
- 235000010633 broth Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- NBQNPNAHCVGAAM-UHFFFAOYSA-N morpholine;sodium Chemical compound [Na].C1COCCN1 NBQNPNAHCVGAAM-UHFFFAOYSA-N 0.000 description 1
- HHCBQFCXIXDWSJ-UHFFFAOYSA-N n-methyl-n-[methyl(trichloromethylsulfanyl)sulfamoyl]methanamine Chemical compound CN(C)S(=O)(=O)N(C)SC(Cl)(Cl)Cl HHCBQFCXIXDWSJ-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000000885 phytotoxic effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZCPSWAFANXCCOT-UHFFFAOYSA-N trichloromethanesulfonyl chloride Chemical compound ClC(Cl)(Cl)S(Cl)(=O)=O ZCPSWAFANXCCOT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
- A01N47/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing >N—S—C≡(Hal)3 groups
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Es ist bekannt, daß bei der Umsetzung von N-monosubstituierten Alkyl- bzw. Arylsulfonsäureamiden mit Trichlormethylsulfenchlorid die entsprechenden Trichlormethylmercaptoverbindungen gebildet werden, die sich durch eine hohe biologische Wirksamkeit auszeichnen. Diese Verbindungen wirken im Sporentest als Blattfungizide, verlieren ihre Wirkung bei Versuchen auf der Pflanze aber weitgehend. Außerdem haben dieseIt is known that in the reaction of N-monosubstituted alkyl or aryl sulfonic acid amides with trichloromethylsulfen chloride the corresponding trichloromethyl mercapto compounds are formed, which are characterized by a high biological effectiveness. These connections act as foliar fungicides in the spore test, lose their effect in tests on the Plant but largely. Also have this
H3C,H 3 C,
H3CH 3 C
Substanzen zum Teil phytotoxische Eigenschaften. Substances partly phytotoxic properties.
Es wurde nun gefunden, daß man bei der Umsetzung von N-substituiertem Sulfamid, das mindestens ι freies Wasserstoffatom am Stickstoff besitzt, mit Trichlormethylsulfenchlorid zu neuen stark fungiziden Verbindungen gelangt. Für den Fall des Trimethylsulfamids verläuft die Reaktion folgendermaßen:It has now been found that in the implementation of N-substituted sulfamide, the at least ι has free hydrogen atom on nitrogen, to new with trichloromethylsulfenchlorid strongly fungicidal compounds. In the case of trimethyl sulfamide, the reaction proceeds as follows:
—SO2-N-H + CIS—CCl3 - SO 2 -NH + CIS-CCl 3
CH,CH,
H3C.H 3 C.
H3CH 3 C
,N-SO9-N-S-CCL, N-SO 9 -NS-CCL
CH3 CH 3
109 704/6109 704/6
Die Umsetzung wird in Gegenwart von Alkalihydroxyden bzw. -carbonaten oder auch tertiären Basen als Salzsäure-Acceptoren durchgeführt. Man arbeitet zweckmäßig in organischen Lösungsmitteln, wie Benzol, Chlorbenzol, Chloroform, doch läßt sich auch in wäßrigem Medium arbeiten.The reaction is carried out in the presence of alkali metal hydroxides or carbonates or else tertiary ones Bases carried out as hydrochloric acid acceptors. It is advisable to work in organic solvents, such as benzene, chlorobenzene, chloroform, but can also be used in an aqueous medium.
Die neuen Verbindungen sollen als Pflanzenschutzmittel verwendet werden. Sie sind bei guter Pflanzenverträglichkeit zum Teil in vivo hervorragend wirksam gegen phytopathogene Eilze. Nachfolgend ist die Wirksamkeit einiger der erfindungsgemäßen Verbindungen gegen den Erreger der Kartoffelkrautfäule (Phytophthora infestans) verzeichnet und ihre Wirksamkeit derjenigen; einiger bereits- bekannter Fungizide, vor allem auf Basis von Alkyl- und Arylsulfonsäuren, gegenübergestellt. Aus diesem Vergleich wird die hohe Wirksamkeit der erfindungsgemäßen Verbindungen deutlich.The new compounds are intended to be used as crop protection agents. You are with good Plant compatibility, partly in vivo, extremely effective against phytopathogenic Eilze. Below is the effectiveness of some of the compounds of the invention against the pathogen the late blight (Phytophthora infestans) and their effectiveness; some already known fungicides all based on alkyl and aryl sulfonic acids. This comparison becomes the high effectiveness of the compounds according to the invention clearly.
Kartoffelpflanzen (holländische Erstlinge) wurden mit wäßrigen Brühen der Präparate in den angegebenen Konzentrationen bespritzt, nach 24 Stunden mit Zoosporangien von Phytophthora infestans künstlich infiziert und in Feuchtkammern gebracht. Am sechsten Tag nach der Infektion wurde der Befall ermittelt und in Prozent des Befalls der unbehandelten Kontrolle, deren Befallsgrad = 100 gesetzt wurde, ausgedrückt. Aus den Befunden der folgenden Tabellen ergibt sich, daß die wirksamsten der erfindungsgemäßen Verbindungen gegen Phytophthora infestans die bisher als die besten bekannten Verbindungen noch übertreffen.Potato plants (Dutch first fruits) were mixed with aqueous broths of the preparations in the specified concentrations, after 24 hours with zoosporangia of Phytophthora infestans artificially infected and placed in humid chambers. On the sixth day after infection the infestation was determined and expressed as a percentage of the infestation of the untreated control, the degree of infection of which was set = 100. From the The following tables show that the most effective of the compounds according to the invention against Phytophthora infestans still surpass those compounds known to date as the best.
Gegenüber kupferhaltigen Fungiziden haben sie zudem den Vorzug, die Entwicklung der Pflanzen nicht nachteilig zu beeinflussen. Neben Phytophthora infestans sind die Verbindungen auch noch gegen andere phytopathogene Pilze, wie Plasmopara viticola an Reben und Septoria apii an Sellerie, gut wirksam.Compared to fungicides containing copper, they also have the advantage that the plants develop not to be adversely affected. In addition to Phytophthora infestans, the compounds are also still against other phytopathogenic fungi such as Plasmopara viticola on vines and Septoria apii Celery, well effective.
i. Vergleichspräparatei. Comparator preparations
0,1% Aufwai
0.1%
0,05% id amount
0.05%
^) Zn
H2C-NH-CS-SH 2 C-NH-CS-S.
^) Zn
H 2 C-NH-CS-S
HC/ 2\CH/ \CH CO
HC / 2 \ CH / \
HC /CH\ /
XH2 XOIJ I ^ NS-CCl 3
HC / CH \ /
XH 2 XO
I (p-Cl) C 6 H 4 -SO 2 -NS-CCl 3
I.
2. Erfindungsgemäße Verbindungen2. Compounds according to the invention
C6H5 I.
C 6 H 5
Beispiel ιExample ι
Zur Suspension von 40 g Trimethylsulfamid-Natrium in 200 ml Benzol tropft man unter starkem Rühren innerhalb von 15 Minuten 46,5 g Trichlormethylsulfenchlorid ein. Hierbei steigt die Temperatur bis etwa 500 an. Man rührt V2 Stunde nach und versetzt die Lösung anschließend mit Wasser. Die benzolische Schicht wird von der wäßrigen Phase getrennt und nach dem Trocknen über Natriumsulfat abgesaugt. Im Vakuum wird sodann die Lösung eingeengt. N-Trichlormethylmercapto-N, N', N'-trimethylsulfamid wird in einer Ausbeute von etwa 55 g erhalten. F. 55 bis 6o° (aus Waschbenzin).To the suspension of 40 g of sodium trimethylsulfamide in 200 ml of benzene, 46.5 g of trichloromethylsulfen chloride are added dropwise with vigorous stirring over the course of 15 minutes. The temperature rises to about 50 ° here . The mixture is stirred for another 2 hours and the solution is then mixed with water. The benzene layer is separated from the aqueous phase and, after drying over sodium sulfate, filtered off with suction. The solution is then concentrated in vacuo. N-Trichloromethylmercapto-N, N ', N'-trimethylsulfamide is obtained in a yield of about 55 g. F. 55 to 60 ° (from petroleum ether).
Beispiel 2
35Example 2
35
10 g N', N'-Dimethyl-N-(2-chlorphenyl)-sulfamid werden in der Lösung von 1,7 g Natriumhydroxyd in 50 ml Wasser in die zugehörige Natriumverbindung übergeführt. Nach vollständiger Auflösung tropft man bei Raumtemperatur die Lösung von 8 g Trichlormethylsulfenchlorid in 20 mg Alkohol ein. Hierbei steigt die Temperatur leicht an. Man rührt etwa 10 Minuten nach und saugt das N-Trichlormethylmercapto-N', N'-dimethyl-N-(2-chlorphenyl)-sulfamid a.b. Ausbeute 13 g. F. 127 bis 1290 (aus Methanol).10 g of N ', N'-dimethyl-N- (2-chlorophenyl) sulfamide are converted into the associated sodium compound in a solution of 1.7 g of sodium hydroxide in 50 ml of water. After complete dissolution, the solution of 8 g of trichloromethylsulfen chloride in 20 mg of alcohol is added dropwise at room temperature. The temperature rises slightly here. The mixture is stirred for about 10 minutes and the N-trichloromethylmercapto-N ', N'-dimethyl-N- (2-chlorophenyl) sulfamide is filtered off with a yield of 13 g. F. 127 to 129 0 (from methanol).
ι log N', N'-Dimethyl-N-phenylsulfamid werden in 50 mg 4%iger wäßriger Natronlauge gelöst und mit der Lösung von 8 g Trichlormethylsulfenchlorid in 20 ml Alkohol versetzt. Nach kurzem Nachrühren saugt man vom ausgefallenen N-Trichlormethylmercapto - N', N' - dimethyl - N - phenyl sulfamid (12 g) ab und kristallisiert aus Methanol um. F. 98 bis ioo°.ι log N ', N'-dimethyl-N-phenylsulfamide be dissolved in 50 mg of 4% strength aqueous sodium hydroxide solution and mixed with the solution of 8 g of trichloromethylsulfen chloride added to 20 ml of alcohol. After stirring for a short time, the precipitated N-trichloromethyl mercapto is sucked off - N ', N' - dimethyl - N - phenyl sulfamide (12 g) and crystallized from methanol around. F. 98 to 100 °.
166 g (Vio Mol) N-Methyl-N', N'-diäthyl-sulfamid werden in einer Lösung von 4 g Natriumhydroxyd in 40 ml Wasser aufgelöst. Unter Rühren gibt man bei Raumtemperatur langsam die Lösung von 12 g Trichlormethylsulfenchlorid in 20 ml166 g (Vio mol) of N-methyl-N ', N'-diethyl sulfamide are dissolved in a solution of 4 g of sodium hydroxide in 40 ml of water. While stirring the solution of 12 g of trichloromethylsulfen chloride in 20 ml is slowly added at room temperature
Alkohol dazu und rührt etwa 1 Stunde nach. Das abgeschiedene öl wird in Äther aufgenommen und die ätherische Lösung nach 'dem Trocknen im Vakuum eingeengt. Hierbei bleibt N-Trichlormethylmercapto-N-methyl - N', N' - diäthyl-sulfamid als rotbraunes öl zurück.Add alcohol and stir for about 1 hour. The separated oil is taken up in ether and the ethereal solution, after drying, concentrated in vacuo. This leaves N-trichloromethylmercapto-N-methyl - N ', N' - diethyl sulfamide as red-brown oil.
!3,5 g N, N-Dimethyl-N'-(2, 4-dichlorphenyl)-sulfamid werden in 200 ecm Wasser unter Zusatz von 2,4 g Natriumhydroxyd gelöst. Unter heftigem Rühren tropft man bei Zimmertemperatur 9,3 g Trichlormethylsulfenchlorid in diese Lösung ein. Hierbei scheidet sich ein öl ab, das man in Benzol aufnimmt, trocknet, mit Tierkohle filtriert und im Vakuum einengt. Das N'-Trichlormethylmercapto-N, N-dimethyl-N'-(2, 4-dichlorphenyl)-sulfamid fällt hierbei kristallin aus. F. 93 bis 960 (aus Waschbenzin).3.5 g of N, N-dimethyl-N '- ( 2,4-dichlorophenyl) sulfamide are dissolved in 200 ecm of water with the addition of 2.4 g of sodium hydroxide. 9.3 g of trichloromethylsulfen chloride are added dropwise to this solution at room temperature with vigorous stirring. An oil separates out, which is taken up in benzene, dried, filtered with animal charcoal and concentrated in vacuo. The N'-trichloromethylmercapto-N, N-dimethyl-N '- (2,4-dichlorophenyl) sulfamide precipitates in crystalline form. F. 93 to 96 0 (from petroleum ether).
11,8g der Natriumverbindung des N, N-Dimethyl-N'-(4-nitrophenyl)-sulfamids werden in 100 ecm Benzol angeschlämmt und in der Siedehitze mit 7 g Trichlormethylsulfenchlorid versetzt. Man rührt kurze Zeit nach, saugt ab und engt das Filtrat im Vakuum ein. Das N'-Trichlormethylmercapto -N1N- dimethyl - N'- (4-nitrophenyl) -sulfamid schmilzt bei 1920.11.8 g of the sodium compound of N, N-dimethyl-N '- (4-nitrophenyl) sulfamide are suspended in 100 ecm of benzene and 7 g of trichloromethylsulfen chloride are added at the boiling point. The mixture is stirred for a short time, filtered off with suction and the filtrate is concentrated in vacuo. The N'-Trichloromethylmercapto -N 1 N-dimethyl-N'- (4-nitrophenyl) -sulfamide melts at 192 0 .
21,8 g N, N-Dimethyl-N'-(4-fluorphenyl)-sulfamid werden in 150 ecm Wasser unter Zusatz von 4 g Natriumhydroxyd in Lösung gebracht. Bei 15 bis 20° tropft man unter starkem Rühren 18,6 g Trichlormethylsulfenchlorid in die Lösung ein. Das N'-Trichlormethylmercapto - N, N-dimethyl-N'-(4-fluorpheny L) -sulfamid fällt hierbei sofort in fester Form aus. F. ioo°.21.8 g of N, N-dimethyl-N '- (4-fluorophenyl) sulfamide are brought into solution in 150 ecm of water with the addition of 4 g of sodium hydroxide. at At 15 ° to 20 °, 18.6 g of trichloromethylsulfen chloride are added dropwise to the solution with vigorous stirring a. The N'-trichloromethyl mercapto - N, N-dimethyl-N '- (4-fluoropheny L) sulfamide is immediately precipitated in solid form. F. ioo °.
49 g der Natriumverbindung des N, N-Dimethyl-N'-(2, 4-dli'methylphenyl) -stilfamidjs werden in ben-49 g of the sodium compound of N, N-dimethyl-N '- (2, 4-d l i'methylphenyl) -stilfamidjs are in ben-
zolischer Lösung in der Siedehitze tropfenweise mit 36,4 g Trichlormethylsulfenchlorid versetzt. Nach der üblichen Aufarbeitung erhält man das N'-Trichlormethylmercapto-N, N-dimethyl-N'-(2, 4-dimethylphenyl) -sulfamid vom F. 70 bis 720..zolischer solution at the boiling point with 36.4 g of trichloromethylsulfen chloride added dropwise. After the usual work-up gives the N'-Trichlormethylmercapto-N, N-dimethyl-N '- (2, 4-dimethylphenyl) -sulfamide, melting at 70 to 72 0 ..
53,9 g der Natriumverbindung des N, N-Dimethyl-N'-(2-äthylphenyl)-sulfamids werden in Toluol bei ioo° mit 40,1 g Trichlormethylsulfenchlorid versetzt. Nach der üblichen Aufarbeitung erhält man das N'-Trichlormethylmercapto-N, N-dimethyl-N'-(2-äthylphenyl)-sulfamid vom F. 78 bis 79°.53.9 g of the sodium compound of N, N-dimethyl-N '- (2-ethylphenyl) sulfamide are in toluene at 100 ° with 40.1 g of trichloromethylsulfen chloride offset. After the usual work-up, the N'-trichloromethylmercapto-N is obtained, N-dimethyl-N '- (2-ethylphenyl) sulfamide with a temperature of 78 to 79 °.
50,9 g der Natriumverbindung des N, N-Di-50.9 g of the sodium compound of the N, N-Di-
ao methyl - N' - (2-äthyl - 6- methyl - phenyl) - sulf ami ds werden bei ioo° in toluolischer Lösung mit 35)9 S Trichlormethylsulfenchlorid versetzt. Das nach üblicher Aufarbeitung erhaltene N'-Trichlormethylmercapto - N, N- dimethyl - N'- (2 - äthyl - 6 - methylphenyl)-sulfamid ist ein Öl, das nicht kristallisiert.ao methyl-N '- (2-ethyl-6-methyl-phenyl) -sulfamides are mixed with 35) 9 S trichloromethylsulfen chloride at 100 ° in a toluene solution. The N'-trichloromethylmercapto-N, N-dimethyl-N'- (2-ethyl-6-methylphenyl) -sulfamide obtained after conventional work-up is an oil which does not crystallize.
3,8 g der Natriumverbindung des N, N-Dimethyl-N'-benzyl-sulfamids werden in siedendem Benzol mit 3 g Trichlocmethylsulfenchlorid zur Reaktion gebracht. Das N'-Trichlormethylmercapto - N, N- dimethyl - N' - benzyl - sulfamid schmilzt bei 60 bis 66°.3.8 g of the sodium compound of N, N-dimethyl-N'-benzyl sulfamide are in boiling benzene with 3 g of Trichlocmethylsulfenchlorid to Brought reaction. The N'-trichloromethyl mercapto - N, N-dimethyl - N '- benzyl - sulfamide melts at 60 to 66 °.
18,8 g der Natriumverbindung des N, N-Dimethyl-N'-(n-propyl)-sulfamids werden in 100 ecm Benzol mit 18,6 g Trichlormethylsulfenchlorid ι Stunde bei 50 bis 6o° gerührt. Man saugt anschließend vom ausgefallenen Natriumchlorid ab und engt das Filtrat im Vakuum ein. Das N'-Trichlormethylmercapto-N, N-dimethyl-N'- (n-propyl) -18.8 g of the sodium compound of N, N-dimethyl-N '- (n-propyl) sulfamide are in 100 ecm of benzene with 18.6 g of trichloromethylsulfen chloride ι hour at 50 to 60 ° stirred. The precipitated sodium chloride is then filtered off with suction and the filtrate is concentrated in vacuo. The N'-trichloromethylmercapto-N, N-dimethyl-N'- (n-propyl) -
sulfamid bleibt als gelbbraunes Öl zurück.sulfamid remains as a yellow-brown oil.
22 g N, N-Dimethyl-N'-(4-methyl-cyclohexyl)-sulfamid werden in roo ecm Wasser unter Zusatz von 4,4 g Natriumhydroxyd gelöst. Bei Zimmertemperatur tropft man dann unter heftigem Rühren die Lösung von 18,6 g Trichlormethylsulfenchlorid in 50 ecm Alkohol zu. Hierbei fällt das Reaktionsprodukt ölig aus. Nach Umlösen aus Methanol zeigt das N'-Trichlormethylmercapto-N, N-dimethyl - N' - (4 - methyl - cyclohexyl) -sulfamid einen Schmelzpunkt von 80 bis 870.22 g of N, N-dimethyl-N '- (4-methyl-cyclohexyl) -sulfamide are dissolved in roo 1 cm of water with the addition of 4.4 g of sodium hydroxide. A solution of 18.6 g of trichloromethylsulfen chloride in 50 ecm of alcohol is then added dropwise at room temperature with vigorous stirring. The reaction product precipitates as an oily product. After dissolving from methanol, the N'-trichloromethylmercapto-N, N-dimethyl-N '- (4-methyl-cyclohexyl) -sulfamide has a melting point of 80 to 87 0 .
15,2g N, N - Dimethyl - N' - (2-methoxy-phenyl) sulfamid werden unter Zusatz von 3 g Natriumhydroxyd in 200 ecm Wasser gelöst. Unter Wasserkühlung tropft man langsam 12,3 g Trichlormethylsulfenchlorid zu. Man rührt 1At Stunde nach und saugt ab. Das N'-Trichlormethylmercapto-N, N - dimethyl - N'- (2 - methoxy - phenyl) - sulfamid zeigt' einen Schmelzpunkt von 125 bis 1270 (aus Methanol).15.2 g of N, N - dimethyl - N '- (2-methoxyphenyl) sulfamide are dissolved in 200 ecm of water with the addition of 3 g of sodium hydroxide. While cooling with water, 12.3 g of trichloromethylsulfen chloride are slowly added dropwise. The mixture is stirred for 1 hour and filtered off with suction. The N'-Trichlormethylmercapto-N, N - dimethyl - N '(2 - methoxy - phenyl) - sulfamide' has a melting point 125-127 0 (from methanol).
15 g Morpholinsulfoanilid-Natrium werden in 150 ecm Benzol mit 10,6 g- Trichlormethylsulfenchlorid versetzt und 1 Stunde bei Zimmertemperatur gerührt. Man saugt anschließend vom Natriumchlorid ab und engt das Filtrat im Vakuum ein. Das Morpholin-sulfo-(N-trichlormethylmercapto-anilid) fällt hierbei kristallin aus. F. 146 bis 1470 (nach Umkristallisation aus Alkohol).15 g of sodium morpholine sulfoanilide are mixed with 10.6 g of trichloromethylsulfen chloride in 150 ecm of benzene and the mixture is stirred at room temperature for 1 hour. The sodium chloride is then filtered off with suction and the filtrate is concentrated in vacuo. The morpholine sulfo- (N-trichloromethylmercapto-anilide) precipitates in crystalline form. F. 146 to 147 0 (after recrystallization from alcohol).
16 g Morpholinsulfo- (4-chloranilid) -Natrium werden in 150 ecm Benzol mit 106 g Trichlormethylsulfenchlorid zur Umsetzung gebracht. Man rührt kurze Zeit nach, saugt vom Natriumchlorid ab und engt die Lösung im Vakuum ein. Das anfallende Morpholin - sulf ο - (N - trichlormethylmercapto-4-chloranilid) schmilzt bei 140 bis 1430.16 g of morpholinesulfo- (4-chloroanilide) sodium are reacted in 150 ecm of benzene with 106 g of trichloromethylsulfen chloride. The mixture is stirred for a short time, the sodium chloride is filtered off with suction and the solution is concentrated in vacuo. The resulting morpholine - sulf ο - (N - trichloromethyl mercapto-4-chloranilide) melts at 140 to 143 0 .
30,5 g Pyrrolidin-sulfoanilid-Natrium werden bei 400 in 200 ecm Benzol mit 22,4 g Trichlormethylsulfenchlorid umgesetzt. Nach kurzem Rühren saugt man vom Natriumchlorid ab und engt die Lösung im Vakuum ein. Das Pyrrolidtn-sulfo-(N-trichlormethylmercapto-anilid) schmilzt bei 117 bis 1190 (nach Umlösen aus Methanol).30.5 g of pyrrolidine-sulfoanilid sodium are reacted at 40 0 in 200 cc of benzene with 22.4 g Trichlormethylsulfenchlorid. After brief stirring, the sodium chloride is filtered off with suction and the solution is concentrated in vacuo. The pyrrolide sulfo- (N-trichloromethylmercapto-anilide) melts at 117 to 119 0 (after dissolving from methanol).
40 g Morpholinsulfoanilid werden in einer Lösung von 6,7 g Natriumhydroxyd in 5°ccm 10S Wasser in die Natriumverbindung übergeführt. Man verdünnt diese wäßrige Lösung mit 30 ecm Methanol, tropft bei Zimmertemperatur langsam 23 g Trichlormethylsulfenchlorid zu und rührt anschließend V2 Stunde lang nach. Hierbei erhält man das N-Trichlormercapto-N, N'-pentamethylen-N-phenyl-sulfamid vom F. 113 bis 1150 (nach Umlösen aus Alkohol).40 g of morpholine sulfoanilide are converted into the sodium compound in a solution of 6.7 g of sodium hydroxide in 5 ° ccm of 10 S water. This aqueous solution is diluted with 30 ecm of methanol, 23 g of trichloromethylsulfen chloride are slowly added dropwise at room temperature and the mixture is then stirred for another 2 hours. In this case, there is obtained the N-Trichlormercapto-N, N'-pentamethylene-N-phenyl-sulfamide, mp 113 to 115 0 (after recrystallising from alcohol).
10 g N, N-Dimethyl-N'-(4-chlorphenyl)-sulfamid werden analog Beispiel 2 zur Umsetzung gebracht. Das N'-Trichlormethylmercapto-N, N-dimethyl-N'-(4-chlorphenyl)-sulfamid hat einen Schmelzpunkt von 100 bis 1030 (nach Umlösen aus Methanol).10 g of N, N-dimethyl-N '- (4-chlorophenyl) sulfamide are reacted analogously to Example 2. The N'-Trichlormethylmercapto-N, N-dimethyl-N '- (4-chlorophenyl) -sulfamide has a melting point of 100-103 0 (after recrystallising from methanol).
21,4 g N, N-Dimethyl-N'-(2-methylphenyl)suIfamid werden in einer Lösung von 4 g Natrium-21.4 g of N, N-dimethyl-N '- (2-methylphenyl) suIfamid are dissolved in a solution of 4 g of sodium
hydroxyd in 8o ecm Wasser unter Zusatz von 2o ecm Methanol aufgelöst und bei Zimmertemperatur tropfenweise mit i8 g Trichlormethylsulfeiichlorid versetzt. Hierbei scheidet sich ein öl ab, das man in Äther aufnimmt. Nach Verdampfen des Äthers hinterbleibt· ein kristalliner Rückstand von N'-Trichlormethylmercapto-N, N-dimethyl-N'-(2-methylphenyl)-sulfamid, das nach dem Umlösen aus Methanol bei 88° schmilzt.hydroxyd dissolved in 8o ecm water with the addition of 2o ecm methanol and at room temperature dropwise with 18 g of trichloromethylsulfonyl chloride offset. Here an oil separates out, which is absorbed in ether. After evaporation of the Ether remains behind a crystalline residue of N'-trichloromethylmercapto-N, N-dimethyl-N '- (2-methylphenyl) sulfamide, which melts at 88 ° after dissolving from methanol.
20,9 g der Natriumverbmdung des N, N-Dimethyl - N' - (1 - naphthyl) - sulf amids werden in 100 ecm Toluol angeschlämmt und bei Zimmertemperatur tropfenweise mit 14,3 g Trichlormethylsulfenchlorid versetzt. Hierbei steigt die Temperatur bis etwa 35 ° an. Man rührt 1 Stunde nach, saugt vom Natriumchlorid ab und engt das Filtrat im Vakuum ein. Hierbei erhält man einen öligen Rückstand, der durch Behandlung mitÄther-Petroläther zum größten Teil kristallisiert Das N'-Trichlormethylmercapto-N, N-dimethyl-N'-(i-naphthyl)-sulfamid schmilzt bei 86 bis 890.20.9 g of the sodium compound of N, N-dimethyl-N '- (1-naphthyl) -sulfamide are suspended in 100 ecm of toluene and 14.3 g of trichloromethylsulfene chloride are added dropwise at room temperature. The temperature rises to about 35 °. The mixture is stirred for 1 hour, the sodium chloride is filtered off with suction and the filtrate is concentrated in vacuo. Here, an oily residue is obtained, which by treatment mitÄther-petroleum ether for the most part crystallized N'-Trichlormethylmercapto-N, N-dimethyl-N '- (i-naphthyl) -sulfamide melts at 86 to 89 0th
20,1 g N, N-Dimethyl-N'-(2-pyridyl)-sulfamid werden unter Zusatz von 4 g Natriumhydroxyd in 200 ecm Wasser gelöst. Bei Zimmertemperatur tropft man zur Lösung unter heftigem Rühren 18,6 g Tricnlormethylsulfenchlorid zu. Hierbei fällt das N'-Trichlormethylmercapto-N, N-dimethyl-N'-(2-pyridyl)-sulfamid sofort in kristalliner Form aus. Nach kurzem Nachrühren wird abgesaugt und der Filterrückstand mit Wasser nachgewaschen. F. 940.20.1 g of N, N-dimethyl-N '- (2-pyridyl) sulfamide are dissolved in 200 ecm of water with the addition of 4 g of sodium hydroxide. At room temperature, 18.6 g of trichloromethylsulfene chloride are added dropwise to the solution with vigorous stirring. The N'-trichloromethylmercapto-N, N-dimethyl-N '- (2-pyridyl) sulfamide precipitates out immediately in crystalline form. After a short further stirring, it is suctioned off and the filter residue is washed with water. F. 94 0 .
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF17281A DE975295C (en) | 1955-04-08 | 1955-04-08 | Process for the preparation of fungicidal derivatives of trichloromethyl mercaptan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF17281A DE975295C (en) | 1955-04-08 | 1955-04-08 | Process for the preparation of fungicidal derivatives of trichloromethyl mercaptan |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE975295C true DE975295C (en) | 1961-11-02 |
Family
ID=7088528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF17281A Expired DE975295C (en) | 1955-04-08 | 1955-04-08 | Process for the preparation of fungicidal derivatives of trichloromethyl mercaptan |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE975295C (en) |
-
1955
- 1955-04-08 DE DEF17281A patent/DE975295C/en not_active Expired
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