CS264978B1 - 2,5,6-Trisubstituted-4-pyrones and processes for their preparation - Google Patents
2,5,6-Trisubstituted-4-pyrones and processes for their preparation Download PDFInfo
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Abstract
Riešenie sa týká nových, fungicídne účinných 2,5,6-trisubstituovaných 4-pyrón všeobecného vzorca I, ktoré sa dajú při pravit reakciou 2-chlórmetyi-5 , 6-disubsti- tuovaného 4-pyrónu všeobecného vzorca VI so zlúčeninou zavaáujúci substituent R^ v prostředí organického ředidla pri teplote 20 až 120°C.The solution concerns new, fungicidally effective 2,5,6-trisubstituted 4-pyrones of the general formula I, which can be prepared by reacting 2-chloromethyl-5,6-disubstituted 4-pyrone of the general formula VI with a compound containing the substituent R^ in an organic solvent environment at a temperature of 20 to 120°C.
Description
(57) Riešenie sa týká nových, fungicídne účinných 2,5,6-trisubstituovaných 4-pyrón všeobecného vzorca I, ktoré sa dajú připravit reakciou 2-chlórmetyi-5,6-disubstituovaného 4-pyrónu všeobecného vzorca VI so zlúčeninou zavaáujúci substituent R^ v prostředí organického ředidla pri teplote ~ 20 až 120 °C.(57) The invention relates to novel, fungicidally active 2,5,6-trisubstituted 4-pyrones of the formula I, which can be prepared by reacting a 2-chloromethyl-5,6-disubstituted 4-pyrone of the formula VI with a compound storing an R 1 substituent. in an organic diluent at ~ 20 to 120 ° C.
CS 264 978 B1CS 264 978 B1
Vynález sa týká 2,5,6-trisubstituovaných 4-pyrónov ako aj spósob ich přípravy. Uvedené zlúčeniny sú fungicídne účinné.The invention relates to 2,5,6-trisubstituted 4-pyrones as well as a process for their preparation. The compounds are fungicidally active.
Z literatúry sú známe 2-[N-/2'-kyanoetyltiokarbamidosulfenylmetyl/]-5-hydroxy-4-pyrón a jeho komplexně zlúčeniny so Zn a Ni ako fungicidy [ US patent 799 945, C. A. 80, 146 018 (1974) ], dalej 2-hydroxymetyl-5-hydroxy-5-/N,N-dialkyltiokarbamosulfenylmetyl-4-pyróny (DOS 2 625 823). Známe sú tiež organofosforové zlúčeniny všeobecného vzorca XI □'2- [N- (2'-cyanoethylthiocarbamidosulfenylmethyl)] - 5-hydroxy-4-pyrone and its complexes with Zn and Ni as fungicides are known in the literature [US Patent 799,945, CA 80,146,018 (1974)], further, 2-hydroxymethyl-5-hydroxy-5- [N, N-dialkylthiocarbamosulfenylmethyl-4-pyrone (DOS 2,625,823). Organophosphorus compounds of the general formula (XI) are also known.
,12 (XI) v ktoron) R8 znamená vodík, alkyl, alkenyl, R9 znamená alkyl, alkenyl, R1 znamená alkyl, 11 12 cykloalkyl, R vodík, alkyl, alkenyl, R znamená vodík, haloalkyl, Y znamená kyslík alebo síru, ktoré sú účinné ako insekticidy a miticítíy £JP patent 6 229 593, C. A. 107, 780 79 (1987)].12 (XI) wherein R 8 is hydrogen, alkyl, alkenyl, R 9 is alkyl, alkenyl, R 1 is alkyl, R 12 is cycloalkyl, R hydrogen, alkyl, alkenyl, R is hydrogen, haloalkyl, Y is oxygen or Sulfur, which are effective as insecticides and miticites (JP JP 6 229 593, CA 107, 780 79 (1987)).
Teraz boli zistené 2,5,6-trissubstituované 4-pyróny všeobecného vzorca IWe have now found 2,5,6-trissubstituted 4-pyrones of formula I
CH,-R v ktorom R znamená vodík, chlór, bróm, R7 znamená skupinu všeobecného vzorca II, III, IV alebo VCH-R wherein R is hydrogen, chloro, bromo, R 7 is a group of formula II, III, IV or V
-S-CII s-S-CII p
<„ (II) iiř* or6 (III)<'(II) ii * or 6 (III)
-S-C-O-R7 (IV)-SCOR 7 (IV)
II sII p
(V)(IN)
4 kde R a R znamenajú rovnaký alebo rózny alkyl s 1 az 4 atomami uhlíka, připadne spolu s atómom dusíka tvoria šesťčlánkový heterocyklický kruh, v ktorom móže byť ako další heteroatóm kyslík, R® znamená etyl alebo skupinu X3R8, kde X3 znamená kyslík alebo síru a R8 znamená alkyl s 1 až 8 atómami uhlíka alebo fenyl, X3 znamená kyslík alebo síru, R® znamená alkyl s 1 až 4 atómami uhlíka alebo fenyl, R znamená alkyl s 1 až 4 atomami uhlíka, alyl a 24 wherein R and R are the same or different alkyl of 1 to 4 carbon atoms, optionally together with the nitrogen atom, form a six-membered heterocyclic ring, which can, as a further heteroatom oxygen-R® is ethyl or a group R 3 X 8, wherein X 3 is O or s and R 8 is alkyl of 1 to 8 carbon atoms or phenyl, X 3 is O or s, R® is C 1 -C 4 alkyl or phenyl, R is alkyl of 1 to 4 carbon atoms, allyl, and 2
R znamená vodík, metyl alebo chloracetyl.R is hydrogen, methyl or chloroacetyl.
Súčasne bol zistený spdsob přípravy zlúčenín všeobecného vzorca I reakciou 2-chlórmetyl-5,6-disubstituovaného pyrónu všeobecného vzorca Vi ch2ciAt the same time, a process for the preparation of compounds of formula I by reacting 2-chloromethyl-5,6-disubstituted pyrone of formula VI ch 2 ci
(VI) , v ktorom R a R majú uz uvedený význam, so zlúčeninou všeobecného vzorca VII, VIII, IX alebo X(VI), wherein R and R are as defined above, with a compound of formula VII, VIII, IX or X
II \=NII \ = N
SWITH
7 + kde R a R majú uz uvedeny vyznám, M znamená sodík, draslík alebo NH^, v prostředí organického ředidla ako je etylalkohol nitril kyseliny octovéj, metylketón, etylacetát, dimetylformamid a pod. pri teplote 20 až 120 °C.Wherein R and R are as previously described, M is sodium, potassium or NH 4 in an organic diluent such as ethyl alcohol, acetic acid nitrile, methyl ketone, ethyl acetate, dimethylformamide, and the like. at 20 to 120 ° C.
Nasledujúce příklady bližšie osvetlujú, ale neobmedzujú predmet vynálezu.The following examples illustrate but do not limit the scope of the invention.
Příklad 1Example 1
2-/N,N-dimetyltiokarbamosulfenylmetyl/-5-hydroxy-4-pyrón2 / N, N-dimetyltiokarbamosulfenylmetyl / 5-hydroxy-4-pyrone
Zmes 0,25 molu 2-chlórmetyl-5-hydroxy-4-pyrónu a 0,3 molu Ν,Ν-dimetylditiokarbamátu, sodného v 300 ml acetonu sa miešala pri refluxe 4 h. Po ukončení reakcie a ochladnutí sa vylúčená tuhá látka odfiltrovala, po vysušení sa rozdrtila s vodou v trecej miske a opStovne vysušila.A mixture of 0.25 mol of 2-chloromethyl-5-hydroxy-4-pyrone and 0.3 mol of sodium Ν, Ν-dimethyldithiocarbamate in 300 ml of acetone was stirred at reflux for 4 h. After completion of the reaction and cooling, the precipitated solid was filtered off, dried, triturated with water in a mortar and dried again.
Získalo sa 54,2 g bielej látky s t, t. 170 až 173 °C, IČ v CHCl^: v /c=o/ 1 cm v/0.H/ 3 420 cm1 54.2 g of white solid, m.p. 170-173 ° C, IR in CHCl 3: v / c = 0/1 cm v / 0 . H / 3420 cm 1
Analýza pre CgH^^NOgS2 (M = 245,29)Analysis for C 9 H 15 N 2 O 2 S (M = 245.29)
Vypoč. /zist.: 4 S 26,14/25,98; 4 N 5,71/5,78;Calculated. found: 4 S 26.14 / 25.98; 4 N 5.71 / 5.78;
Příklad 2Example 2
2-/0-metyltiokarbsulfenylmetyl/-5-hydroxy-4-pyrón2/0-metyltiokarbsulfenylmetyl / 5-hydroxy-4-pyrone
Z 0,1 molu 2-chlórmetyl-5-hydroxy-4-pyrónu a 0,11 molu O-metylxantogenátu sodného v 150 ml metanolu sa postupom ako v příklade 1 připravilo 14 g bielej látky s t. t, 108,0 °C.From 0.1 mole of 2-chloromethyl-5-hydroxy-4-pyrone and 0.11 mole of sodium O-methylxanthate in 150 ml of methanol, 14 g of a white solid were prepared as in Example 1. mp 108.0 ° C.
Analýza pre CgHgO^S2 (M= 232,26)Analysis for C 8 H 8 O 2 S 2 (M = 232.26)
Vypoč. /zist.: % S 26,30/25,98Calculated. found:% S 26.30 / 25.98
Příklad 3Example 3
Etylén-bis-2-/tiokarbamosulfenylmetyl/-5-hydroxy-4-pyrónEthylene-bis-2 / tiokarbamosulfenylmetyl / 5-hydroxy-4-pyrone
Z 0,1 molu 2-chlórmetyl-5-hydroxy-4-pyrónu a 0,05 molu sodnej soli etylén-bis-ditiokarbamidanu sodného v 100 ml metyletylketónu sa postupom ako v příklade 1 připravilo 14,8 g žlto-hnedej látky s t. t. láo až 183 °C.From 0.1 mole of 2-chloromethyl-5-hydroxy-4-pyrone and 0.05 mole of sodium ethylene-bis-dithiocarbamidate in 100 ml of methyl ethyl ketone, 14.8 g of a yellow-brown solid was prepared as in Example 1. . t. m.p. to 183 ° C.
Analýza pre ci4Hi6N2°6S4 (M = 460,53)Analysis for c 14 H 16 N 2 ° 6 S 4 (M = 460.53)
Výp. /zist. % S 27,84/27,62; % N 6,10/5,81;PDF. / Check. % S 27.84 / 27.62; % N 6.10 / 5.81;
Příklad 4Example 4
2-/0,0-dimetyltiofosforylsulfenylmetyl/-5-metoxy-4-pyrón 2- / 0,0-dimetyltiofosforylsulfenylmetyl / 5-methoxy-4-pyrone
Zmes 0,05 molu 2-chlórmetyl-5-metoxy-4-pyrónu a 0,05 molu sodnej soli 1,2,4-triazolu v 80 ml acetonitrilu sa miešala pri teplote varu 6 h, přidalo sa aktivně uhlie, odfiltrovala sa, rozpúšťadlo sa oddělilo za zniženého tlaku. Získalo sa 6,7 g viskóznej kvapaliny.A mixture of 0.05 mole of 2-chloromethyl-5-methoxy-4-pyrone and 0.05 mole of 1,2,4-triazole sodium salt in 80 ml of acetonitrile was stirred at boiling point for 6 h, charcoal was added, filtered off, the solvent was removed under reduced pressure. 6.7 g of a viscous liquid were obtained.
Analýza pre CgHgNjOj (M = 207,10)Analysis for C 8 H 9 N 3 O 3 (M = 207.10)
Vyp. (zist.: % C 49,22/49,48; i H 4,38/4,40; % N 20,28/20,12Off. (Found:% C 49.22 / 49.48; 1H 4.38 / 4.40;% N 20.28 / 20.12)
Příklad 5Example 5
2-/N,N-dimetyltiokarbamosulfenylmetyl/5-metoxy-4-pyrón2 / N, N-dimetyltiokarbamosulfenylmetyl / 5-methoxy-4-pyrone
Z 0,05 molu 2-chlórmetyl-5-metoxy-4-pyrónu, 0,065 molu sodnej soli N,N-dímetyldítíokarbamidovej kyseliny a 80 ml acetonitrilu sa postupom ako v příklade 4 připravilo 7,1 g bielej látky s t. t. 188,5 °C.From 0.05 mole of 2-chloromethyl-5-methoxy-4-pyrone, 0.065 mole of N, N-dimethyldithiocarbamic acid sodium salt and 80 ml of acetonitrile, 7.1 g of a white solid were prepared as in Example 4. t. 188.5 ° C.
IČ v CHC13 ·. v ic=01 1 642 cm-1 IR in CHC1 3 ·. vi c = 0 1 1642 cm -1
Analýza pre C θ H-^-jNO-j S 2 (M = 259, 32) výp, /zist.: % S 24,72/25,26; % N 5,40/5,43Analysis for C 6 H 11 N 3 O 2 S 2 (M = 259, 32) calcd, found:% S 24.72 / 25.26; % N 5.40 / 5.43
Príklad6Example 6
2-/0,O-dietyltiofosforylsulfenylmetyl/-5-metoxy-4-pyrón2/0, O-dietyltiofosforylsulfenylmetyl / 5-methoxy-4-pyrone
Z 0,05 molu 2-chlórmetyl-5-metoxy-4-pyrónu a 0,04 molu sodnej soli Ο,Ο-dietylditiofosforečnej kyseliny v 60 ml acetonitrilu sa postupom ako v příklade 4 připravilo 6,5 g viskóznej kvapaliny.6.5 g of a viscous liquid were prepared from 0.05 mole of 2-chloromethyl-5-methoxy-4-pyrone and 0.04 mole of Ο, Ο-diethyldithiophosphoric acid sodium salt in 60 ml of acetonitrile.
Analýza pre C33H3^OgPS2 (M = 324,33)Analysis for C 33 H 3 O 6 O 2 PS 2 (M = 324.33)
Vyp. /zast.: % P 9,55/9,88; % S 19,76/20,17Off. %:% P 9.55 / 9.88; % S 19.76 / 20.17
Příklad 7Example 7
2-/0,0-dimety ltio fosfory lsul feny lme ty l/-'5-hydroxy-4-pyrón2- / 0,0-Dimethylphosphorylsulphenylmethyll-5-hydroxy-4-pyrone
Z 0,04 molu 2-chlórmetyl-5-hydroxy a 0,044 molu sodnej soli O,O-diamilditiofosforečnej kyseliny v 60 ml acetonitrilu sa postupom ako v příklade 4 připravilo 12,5 g viskóznej kvapaliny.12.5 g of a viscous liquid were prepared from 0.04 mol of 2-chloromethyl-5-hydroxy and 0.044 mol of sodium O, O-diamildithiophosphoric acid in 60 ml of acetonitrile as described in Example 4.
Analýza pre c|gH27®5í>S2 (M = 394,46)Analysis for C 18 H 27 R 5 S 2 (M = 394.46)
Vyp. /zist.: % P 7,85/8,02; % S 16,26/16,51Off. found:% P 7.85 / 8.02; % S 16.26 / 16.51
Příklad 8Example 8
2-/0-etyl-S-etylfosforylsulfenylmetyl/-5-hydroxy-4-pyrón2/0-ethyl S-etylfosforylsulfenylmetyl / 5-hydroxy-4-pyrone
Z 0,04 molu 2-chlórmetyl-5-hydroxy-4-pyrónu, 0,044 molu sodnej soli 0,5-dietylditiofosforečnej kyseliny a 70 ml metyletylketónu sa postupom ako v příklade 4 připravilo 4,9 g bielej tuhej látky s t. t. 149,1 °C.From 0.04 mol of 2-chloromethyl-5-hydroxy-4-pyrone, 0.044 mol of 0.5-diethyldithiophosphoric acid sodium salt and 70 ml of methyl ethyl ketone, 4.9 g of a white solid was prepared as in Example 4. t. 149.1 ° C.
Analýza pre C3qH33O3PS2 (M = 310,31)Analysis for C 3 H 33 O 3 PS 2 (M = 310.31)
Vyp. /zist.: % P 9,99/9,69; 4 S 20,68/21,09Off. found:% P 9.99 / 9.69; 4 S 20.68 / 21.09
Příklad 9Example 9
2-/0-etyl-0-izopropylfosforylsulfenylmetyl/-5-hydroxy-4-pyrón z 0,04 molu 2-chlórmetyl-5-hydroxy-4-pyrónu, 0,044 molu sodnej soli O-etyl-S-isopropyltiofosforečnej kyseliny a 80 ml metyletylketonu sa postupom ako v přiklade 4 připravilo 9,8 g viskóznej kvapaliny.2- (O-ethyl-O-isopropylphosphorylsulfenylmethyl) -5-hydroxy-4-pyrone from 0.04 moles of 2-chloromethyl-5-hydroxy-4-pyrone, 0.044 moles of O-ethyl-S-isopropylthiophosphoric acid sodium salt and 80 ml of methyl ethyl ketone was prepared as in Example 4 to give 9.8 g of a viscous liquid.
IČ v CHClj:v^coy 1 720 cm 1 360 cm S 3 430 cm 1 IR in CHCl₃: in which y ^ 1 1 720 cm 360 cm 430 cm N 3 1
Analýza pre C-^H^OgPS (M = 308,27)Analysis for C- ^H ^OgPS (M = 308.27)
Vyp. (zist.: i P 10,04/10,28; % S 10,40/10,61Off. (found: P 10.04 / 10.28;% S 10.40 / 10.61
Příklad 10Example 10
2-/0,0-difenyltiofosforylsulfenylmetyl/-5-hydroxy-4-pyrón2- / 0,0-difenyltiofosforylsulfenylmetyl / 5-hydroxy-4-pyrone
Z 0,03 molu 2-chlórmetyl-5-hydroxy-4-pyrónu a 0,033 molu draselnej soli O,O-difenylditofosforečnej kyseliny v 60 ml acetonitrilu sa postupom ako v příklade 4 připravilo 8,3 g bielej kryštalickej látky s t. t· 124,1 °c.From 0.03 mole of 2-chloromethyl-5-hydroxy-4-pyrone and 0.033 mole of O, O-diphenyldithophosphoric acid potassium salt in 60 ml of acetonitrile, 8.3 g of a white crystalline solid were obtained as in Example 4. mp 124.1 ° c.
Analýza pre c18H15O5pS2 (M = 406,29)Analysis for c 18 H 15 O 5 p S 2 (M = 406.29)
Vyp. (zist.: % P 7,62/7,78; % S 15,77/16,18Off. (found:% P 7.62 / 7.78;% S 15.77 / 16.18
Příklad 11Example 11
2-/O-etyletyltiofosforylsulfenylmetyl/-5-hydroxy-4-pyrón2 / O-etyletyltiofosforylsulfenylmetyl / 5-hydroxy-4-pyrone
Z 0,03 molu 2-chlórmetýl-5-hydroxy-4-pyrónu a 0,033 molu draselnej soli O-etyl-etylditiofosforovej kyseliny v 60 ml metyletylketónu sa postupom ako v příklade 4 připravilo 6,2 g bielej látky s t. t. 110,3 °C.From 0.03 mol of 2-chloromethyl-5-hydroxy-4-pyrone and 0.033 mol of O-ethyl-ethyldithiophosphoric acid potassium salt in 60 ml of methyl ethyl ketone, 6.2 g of white solid was prepared as in Example 4. t. 110.3 ° C.
Analýza pre cioHi504PS2 (M = 294,31)Analysis for c 10 H 15 O 4 PS 2 (M = 294.31)
Vyp. /zist.: % P 10,52/.10,95,- % S 21,78/22,18Off. found:% P 10.52 / .10.95% S 21.78 / 22.18
Příklad 12Example 12
2-/0,O-dimetyltiofosforylsulfenylmetyl/-5-hydroxy-4-pyrón2/0, O-dimetyltiofosforylsulfenylmetyl / 5-hydroxy-4-pyrone
Z 0,03 molu 2-chlórmetyl-5-hydroxy-4-pyrónu a 0,033 molu sodnej soli O,O-dimetylditiofosforečnej kyseliny v 60 ml acetonitrilu sa postupom ako v přiklade 4 připravilo 6 g bielej kryštalickej látky s t. t. 165,4 °C.From 0.03 mole of 2-chloromethyl-5-hydroxy-4-pyrone and 0.033 mole of O, O-dimethyldithiophosphoric acid sodium salt in 60 ml of acetonitrile, 6 g of a white crystalline solid was obtained as in Example 4. t. 165.4 ° C.
IČ v CHC13: v/c=0/ 1 640 cm”1; v/q-h/ 3 420 cm 1 IR in CHC1 3: I / C = 0/1 640 cm "1; in / QH / 3420 cm @ -1
Analýza pre CgH330gPS2 (M = 282,25)Analysis for C 9 H 33 0gPS 2 (M = 282.25)
Vyp. /zist.: % P 10,97/10,70; % S 22,72/21,92Off. found:% P 10.97 / 10.70; % S 22.72 / 21.92
Příklad 13Example 13
2-/O, O-die ty ltio fosfory lsul feny limety l/-5-hydroxy-4-pyrón2- / O, O-diethylphosphorus lsul bitches lime -5-hydroxy-4-pyrone
Z 0,02 molu 2-chlórmetyl-5-hydroxy-4-pyrónu, 0,022 molu sodnej soli Ο,Ο-dietylditiofosforečnej kyseliny a 60 ml acetonu sa postupom ako v příklade 4 připravilo 5,4 g bielej kryštalickej látky s t. t. 109,0 °C.From 0.02 mole of 2-chloromethyl-5-hydroxy-4-pyrone, 0.022 mole of Ο, Ο-diethyldithiophosphoric acid sodium salt, and 60 ml of acetone, 5.4 g of a white crystalline solid were obtained as in Example 4. t. 109.0 ° C.
Analýza pre C10H15O5PS2 (M - 310,31)Analysis for C 10 H 15 O 5 PS 2 (M - 310.31)
Vyp. /zist.: % P 9,98/10,24; % S 20,66/20,86Off. found:% P 9.98 / 10.24; % S 20.66 / 20.86
Příklad 14Example 14
2-/N,N-dietyltiokarbamosulfenylmetyl/5-hydroxy-4-pyrón2 / N, N-dietyltiokarbamosulfenylmetyl / 5-hydroxy-4-pyrone
Z 0,02 molu 2-chlórmetyl-5-hydroxy-4-pyrónu a 0,022 molu sodnej soli N,N-dietylditiokarbamidovej kyseliny v 60 ml acetonu sa postupom ako v příklade 4 připravilo 2,6 g bielej kryštalickej látky s t. t. 116,2 °C.From 0.02 mole of 2-chloromethyl-5-hydroxy-4-pyrone and 0.022 mole of N, N-diethyldithiocarbamic acid sodium salt in 60 ml of acetone, 2.6 g of a white crystalline solid was obtained as in Example 4. t. 116.2 ° C.
Analýza pre (M - 273,45)Analysis for (M - 273,45)
Vyp. /zist.: « N 5,12/5,08; « S 23,45/23,74Off. found: N 5.12 / 5.08; «S 23.45 / 23.74
Příklad 15Example 15
2-/1,2,4-triazolylmetyl/-5-metoxy-4-pyrón2- / 1,2,4-triazolylmethyl / 5-methoxy-4-pyrone
Z 0,05 molu 2-chlórmetyl-5-metoxy-4-pyrónu a 0,05 molu sodnej soli 1,2,4-tiazolu v 80 ml acetonitrilu sa postupom ako v příklade 4 připravilo 4,2 g bielej kryštalickej látky s t, t. 12,6 °C.From 0.05 mole of 2-chloromethyl-5-methoxy-4-pyrone and 0.05 mole of 1,2,4-thiazole sodium salt in 80 ml of acetonitrile, 4.2 g of white crystalline solid was prepared as in Example 4, m.p. t. 12.6 ° C.
Analýza pre CgHgNgOj (M = 207,19)Analysis for C 8 H 9 N 6 O 3 (M = 207.19)
Vyp. /zist.: i C 49,22/49,48; % H4 38/4,40; » N 20,28/20,12Off. found: C 49.22 / 49.48; % H4 38 / 4.40; N 20.28 / 20.12
Přiklad 16 zExample 16 of
2-/N,N-dimetyltiokarbamosulfenylmetyl/-5-chlóracetoxy-4-pyrón /2- (N, N-dimethylthiocarbamosulfenylmethyl) -5-chloroacetoxy-4-pyrone]
K 0,03 ijolu 2-/N,N-dimetyltiokarbamosulfenylmetyl/-5-hydroxy-4-pyrónu a 0,033 molu trietylamínu v 80 ml toluénu sa za miešania přidalo 0,33 molu chloracetylchloridu počas 20 min pri tepl.oťe od 20 do 30 °C. V miešaní sa pokračovalo 2 h pri teplote 60 °C, po ochladnutí sa reakčná zmes premyla 3x50 ml vody, toluénová vrstva sa vysušila a toluén sa oddestiloval za zníženého tlaku. Získalo sa 6,8 g nažltlej tuhej látky s t. t. 182,8 C.To 0.03 µl of 2- (N, N-dimethylthiocarbamosulfenylmethyl) -5-hydroxy-4-pyrone and 0.033 mol of triethylamine in 80 ml of toluene was added with stirring 0.33 mol of chloroacetyl chloride over 20 min at 20-30 ° C. C. Stirring was continued for 2 h at 60 ° C, after cooling, the reaction mixture was washed with 3x50 mL of water, the toluene layer was dried and the toluene was distilled off under reduced pressure. 6.8 g of a yellowish solid with m.p. t. 182.8 C.
Analýza pre cníii2C''-NO4S2 (M = 321,76)Analysis for C n II I 2 C '' - NO 4 S 2 (M = 321.76)
Vyp. /zast.: % Cl 11,0/11,2; % N 4,35/4,6; % S 19,90/20,12Off. / rep:% Cl 11.0 / 11.2; % N 4.35 / 4.6; % S 19.90 / 20.12
Příklad 17Example 17
2-/N,N-dimetyltiokarbamosulfenylmetyl/-5-hydroxy-6-bróm-4-pyrón2 / N, N-dimetyltiokarbamosulfenylmetyl / 5-hydroxy-6-bromo-4-pyrone
Z 0,05 molu 2-chlórmetyl-5-hydroxy-6-bróm-4-pyrónu a 0,06 molu sodnej soli N,N-dimetylditiokarbamidovej kyseliny v 60 ml metyletylketónu sa postupom ako v přiklade 4 připravilo 11,8 g bielej kryštalickej látky s t. t. 169 °C.From 0.05 mole of 2-chloromethyl-5-hydroxy-6-bromo-4-pyrone and 0.06 mole of N, N-dimethyldithiocarbamic acid sodium salt in 60 ml of methyl ethyl ketone, 11.8 g of white crystalline solid was prepared as in Example 4. substances with t. t. Mp 169 ° C.
Analýza pre CgH1gBrNOgS2 (M = 324,20)Analysis for C 8 H 1 gBrNOgS2 (M = 324.20)
Výp. /zist.: % N 4,32/4,13; % Br 24,65/24,71; % S 19,78/19,92PDF. found:% N 4.32 / 4.13; % Br 24.65 / 24.71; % S 19.78 / 19.92
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