CS266986B1 - A method for preparing N- (2,6-dialkylphenyl) -N'-arenesulfonylureas - Google Patents
A method for preparing N- (2,6-dialkylphenyl) -N'-arenesulfonylureas Download PDFInfo
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Abstract
Riešenie sa týká spósobu pripravy N- -/2,6-dialkylfenyl/-N*-arénsulfonylmočovín všeobecného vzorca I reakciou derivátu 2,6-dialkylanilínu všeobecného vzorca II s arénsulfonylizokyanátom všeobecného vzorca III v prostředí inertného aprotického rozpúšťadla pri teplote do 120 °C. Riešenie je možné využiť v chemickom priemysle.The solution relates to a method for preparing N- -/2,6-dialkylphenyl/-N*-arenesulfonylureas of general formula I by reacting a 2,6-dialkylaniline derivative of general formula II with an arenesulfonylocyanate of general formula III in an inert aprotic solvent at a temperature of up to 120 °C. The solution can be used in the chemical industry.
Description
CS 266 986 B1
Vynález sa týká spĎsobu přípravy N-/2,6-dialkylfenyl/N-'-arénsulfonylmočovín. Tietozlúčeniny je možné použit ako herbicidy.
Sulfonylmočoviny odvodené od sulfónamidov a heterocyklických amínov ako sú aminotriazínya aminopyrimidíny sú z literatúry známe (Houben-Weyls Methoden der organischen Chemie, 4.vydanie, zvSzok E 4, Georg Thieme Verlag, Stuttgart 1983, str. 400 až 402). Viaceré zo zlúče-nín tejto skupiny majú herbicídne, připadne farmakologické vlastnosti. Niektoré deriváty2,6-dialkylanilínov opásali Atanasov A. I. a spol. (Synthesis 8, 734 až 736, 1987) a připra-vili ich rozkladom trichlóracetanilidov lúhom v přítomnosti sulfónamidov. Nevýhoda tohotospĎsobu spočívá v tom, že ide o viacstupňovú syntézu a že umožňuje dosahovat iba priemernévýtažky.
Teraz sa zistilo, že N-/2,6-dialkylfenyl/-N'-arénsulfonylmočoviny všeobecného vzorca I
.CONHSO /1/ kde znamená r! vodík, chlor alebo metyl, 2 3 R a R metyl alebo etyl, 4 R vodík, acetyl alebo chloracetyl
je možné připravit reakciou derivátu 2,6-dialkylanilínu všeobecného vzorce II NH-R4 /11/ 2 3 4
kde R , R a R majú už uvedený význam s arénsulfonylizokyanátom všeobecného vzorca III 1 /111/ so2nco kde r! má už uvedený význam v prostředí inertného aprotického organického rozpúštadla ako je benzén, toluén, xylén,dichlórmetán, chloroform, acetonitril, tetrahydrofurán pri teplote do 120 C.
Zistilo sa tiež, že uvedenú reakciu je možné katalyzovat terciárnymi amínmi ako jetrietylamín, pyridin a iné. Získané produkty sú vSčšinou v reakčnom prostředí za studená nerozpustné a dajú saz něho izolovat napr. odsátím. Rozpustné konečné produkty je možné izolovat z reakčnej zmesizahuštěním a kryštalizáciou. Výhodou spósobu podlá vynálezu v porovnaní so známými spósobmi spočívá najma v jehojednoduchosti a vysokých výťažkoch. 2 3 4 y z
Medziprodukty všeobecného vzorca II, kde R , R a R majú už uvedený význam, je možnépřipravit známými postupmi (J. Am. Chem. Soc. 43, 282, 1943; Ber. 73, 1 377, 1940; Ark.
Kemi 22 A, No 18, 4, 1946). Medziprodukty všeobecného vzorca III, kde R1 má už uvedený význam,je možné připravit napr. reakciou arénsulfónamidov s fosgénom (US 3 371 114, De 2 152 971,Dlbrich a spol.: Angew. Chemie 78, 761, 1966) alebo reakciou arénsulfónamidov s chlórsulfonyl-izokyanátom (DE 1 289 526). CS 266 986 B1 3
Nasledujúce příklady ilustrujú ale neobmedzujú predmet vynálezu. Příklad 1 K 3,6 g (0,03 molu) 2,6-dimetylanilínu v 20 ml bezvodého benzénu za intenzívneho mieša-nia přidalo 6,5 g (0,03 molu) o-chlórbenzénsulfonylizokyanátu v 20 ml benzéne. V dfisledkuexotermickej reakcie teplota reakčnej zmesi sa zvýšila až na 45 °C, pričom začal vypadávatprodukt, ktorý sa po 1 hodinovom miešaní reakčnej zmesi odsál, premyl benzénom a vysušil.Získalo sa 9,0 g (89 %) N-/2,6-dimetylfenyl/-N'-o-chlórbenzénsulfonylmočoviny s t. t. 177,7 °C.
Pre C15 H15 Cl N2C>3 S (m. h. 338,91): vypočítané: % C 53,16; % H 4,46; % N 8,27; % S 9,46 zistené: % C 53,28; % H 4,50; % N 8,06; % S 9,90. Příklad 2 K 5,64 g (0,025 molu) 2-metyl-6-etyl-alfa-chlóracetanilidu v 20 ml bezvodého benzénusa přidalo 4,58 g (0,025 molu) benzénsulfonylizokyanátu a zmes sa zahrievala pod refluxom2 h. Po ochladení sa z reakčnej zmesi izolovalo 4,3 g (42 %) vykrystalizovanéj N-/2-metyl--6-etylfenyl/-N-chlóracetyl-N'-benzénsulfonylmočoviny, ktorá po kryštalizácii z chloriduuhličitého mala t. t. 117,3 °C.
Pre C18 H19 Cl N2C>4 S (m. h. 408,92); vypočítané: % C 55,80; % H 5,18; % N 6,85; % S 7,84 zistené: % C 56,0; % H 5,3; % N 6,6; % S 7,3
Postupmi podlá příkladu 1 a 2 boli pri rfiznych reakčných teplotách dalšie zlúčeninyvšeobecného vzorca I, ktoré sú opísáné v nasledujúcej tabulke.
Tabulka
Zlúčenina T. t. °c Výfažok % Molárna hmot- nost Analýza z i stené/vypočíta-né % C % H % N % S N-/2,6-dietylfenyl/-N'-p-toluen- 185,6 80 346,45 62,7 6,4 8,1 8,8 sulfonylmočovina 62,40 6,40 8,09 9,25 N-/2-metyl-6-etylfenyl/-N'-p- 188,6 84,6 332,42 61,42 6,06 8,43 9,64 -toluénsulfonylmočovina 61,3 6,1 8,4 9,3 N-/2,6-dimetylfenyl/-N”-p-toluén- 170,5 55 318,39 60,1 5,76 8,7 9,8 sulfonylmočovina 60,36 5,70 8,80 10,07 K-/2,6-dietylfenyl/-N-o-toluén- 147,0 82 346,45 60,6 6,5 7,9 9,0 sulfonylmočovina 62,40 6,40 8,09 9,25 N-/2,6-dimetylfenyl/-N-o-toluén- 171,3 89 318,39 59,7 5,7 8,7 10,- sulfonylmočovina 60,36 5,70 8,80 10,07 N-/2-metyl-6-etylfenyl/-N-o-toluén~ 161,7 70 332,42 61,2 6,1 8,5 9,3 sulfonylmočovina 61,42 6,06 8,43 9,64 N-/2, 6-dietylfenyl/-N'-o-chlór- 162,3 82 366,87 55,6 5,6 7,6 8,8 benzénsulfonylmočovina 55,66 5,22 7,64 8,74 N-/2-metyl-6-etylfenyl/-N'-o-chlór- 166,7 77 352,84 55,6 5,1 7,9 9,5 benzénsulfonylmočovina 55,47 4,86 7,94 9,07 N-/2-metyl-6~etylfenyl/-N'-benzén- 205,8 83 318,39 60,5 5,7 8,8 10,3 sulfonylmočovina 60,36 5,70 8,80 10,07
CS 266 986 B1
The present invention relates to a process for the preparation of N- (2,6-dialkylphenyl) N-arenesulfonylurea. The thio compounds can be used as herbicides.
Sulfonylureas derived from sulfonamides and heterocyclic amines such as amino triazine aminopyrimidines are known from the literature (Houben-Weyls Methoden der organischen Chemie, 4th edition, publication E 4, Georg Thieme Verlag, Stuttgart 1983, pp. 400-402). Several of the compounds of this group possess herbicidal or pharmacological properties. Some derivatives of 2,6-dialkylanilines have been wrapped in Atanas AI et al. (Synthesis 8: 734-736, 1987) and prepared by digesting trichloroacetanilides with lye in the presence of sulfonamides. The disadvantage of this method is that it is a multi-stage synthesis and that it allows only average yields.
It has now been found that N- (2,6-dialkylphenyl) -N'-arenesulfonylureas of formula (I)
.CONHSO / 1 / where r means! hydrogen, chlorine or methyl, R 3 and R 4 methyl or ethyl, 4 R hydrogen, acetyl or chloroacetyl
can be prepared by reacting a 2,6-dialkylaniline derivative of formula II with NH-R 4/11/2 3 4
wherein R, R and R are as defined above with an arenesulfonyl isocyanate of formula III 1/111 / so2nco wherein r 1 is R 1; as defined above in an inert aprotic organic solvent such as benzene, toluene, xylene, dichloromethane, chloroform, acetonitrile, tetrahydrofuran at a temperature of up to 120 ° C.
It has also been found that this reaction can be catalyzed by tertiary amines such as jet triethylamine, pyridine and others. The products obtained are generally cold insoluble in the reaction medium and can be isolated by, for example, suction. Soluble end products can be isolated from the reaction by concentration and crystallization. The advantage of the method according to the invention compared to the known methods lies in its simplicity and high yields. 2 3 4 yz
Intermediates of formula II wherein R, R and R are as defined above can be prepared by known procedures (J. Am. Chem. Soc. 43, 282, 1943; Ber. 73, 1377, 1940; Ark.
Kemi 22 A, No 18, 4, 1946). Intermediates of formula (III) wherein R 1 is as defined above may be prepared, for example, by reacting arenesulfonamides with phosgene (U.S. Pat. No. 3,371,114, De 2 152 971, Dlbrich et al. chlorosulfonyl isocyanate (DE 1 289 526). CS 266 986 B1 3
The following examples illustrate but do not limit the invention. Example 1 To 3.6 g (0.03 mol) of 2,6-dimethylaniline in 20 ml of anhydrous benzene was added 6.5 g (0.03 mol) of o-chlorobenzenesulfonyl isocyanate in 20 ml of benzene under vigorous stirring. In the following exothermic reaction, the temperature of the reaction mixture was raised to 45 ° C, starting to precipitate the product which was filtered off with suction, washed with benzene after 1 hour of stirring of the reaction mixture and dried. 9.0 g (89%) of N- / 2,6- dimethylphenyl (N'-o-chlorobenzenesulfonylurea, mp 177.7 ° C).
For C 15 H 15 Cl N 2 C 3 S (mh 338.91): calculated:% C 53.16; % H, 4.46; % N, 8.27; % S, 9.46 found:% C, 53.28; % H, 4.50; % N, 8.06; % S 9.90. Example 2 To 5.64 g (0.025 mol) of 2-methyl-6-ethyl-alpha-chloroacetanilide in 20 ml of anhydrous benzene, 4.58 g (0.025 mol) of benzenesulfonyl isocyanate were added and the mixture was heated under reflux for 2 h. 4.3 g (42%) of crystallized N- [2-methyl-6-ethylphenyl] -N-chloroacetyl-N ' -benzenesulfonylurea were isolated, m.p. 117.3 ° C after crystallization from carbon tetrachloride.
For C 18 H 19 Cl N 2 C 4 S (mh 408.92); calculated:% C, 55.80; % H, 5.18; % N 6.85; % S 7.84 found:% C 56.0; % H, 5.3; % N 6.6; % S 7.3
In accordance with the procedures of Examples 1 and 2, other compounds of Formula I, as described in the following Table, were available at the various reaction temperatures.
Table
Compound T. m.p. Yield% Molar mass Analysis Analysis / Calculated% C% H% N% N N- (2,6-diethylphenyl) -N'-p-toluene 185.6 80 346 , 45 62.7 6.4 8.1 8.8 sulfonylurea 62.40 6.40 8.09 9.25 N- (2-methyl-6-ethylphenyl) -N'-p- 188.6 84.6 332,42 61,42 6,06 8,43 9,64 -Toluenesulfonylurea 61,3 6,1 8,4 9,3 N- (2,6-dimethylphenyl) -N-p-toluene-170,5 55 318,39 60,1 5,76 8,7 9,8 Sulfonylurea 60,36 5,70 8,80 10,07 K- (2,6-Diethylphenyl) -No-toluene- 147,0 82 346,45 60 , 6 6.5 7.9 9.0 sulfonylurea 62.40 6.40 8.09 9.25 N- (2,6-dimethylphenyl) -No-toluene 171.3 89 318.39 59.7 5 7 8,7 10, - sulphonylurea 60,36 5,70 8,80 10,07 N- / 2-methyl-6-ethylphenyl / -No-toluene ~ 161,7 70 332,42 61,2 6,1 8 , 5 9,3 sulfonylurea 61,42 6,06 8,43 9,64 N- (2,6-diethylphenyl) -N'-o-chloro-162,3 82 366,87 55,6 5,6 7, 6 8,8 benzenesulfonylurea 55,66 5,22 7,64 8,74 N- (2-methyl-6-ethylphenyl) -N'-o-chloro-166,7 77 352,84 55,6 5,1 7 , 9 9,5 benzenesulfonylurea 55,47 4,86 7,94 9,07 N- / 2-methyl-6-ethylphen yl / -N'-benzene- 205.8 83 318.39 60.5 5.7 8.8 10.3 sulfonylurea 60.36 5.70 8.80 10.07
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