CS272880B1 - Derivatives of 5-hydroxy-2 (hydroxymethyl)-4h-pyran-4-on and method of their preparation - Google Patents

Derivatives of 5-hydroxy-2 (hydroxymethyl)-4h-pyran-4-on and method of their preparation Download PDF

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CS272880B1
CS272880B1 CS47789A CS47789A CS272880B1 CS 272880 B1 CS272880 B1 CS 272880B1 CS 47789 A CS47789 A CS 47789A CS 47789 A CS47789 A CS 47789A CS 272880 B1 CS272880 B1 CS 272880B1
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pyran
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Miroslav Ing Csc Veverka
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Veverka Miroslav
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Abstract

The invention concerns 5-acyl derivatives of 5-hydroxy-2-(hydroxymethyl)-4H-pyran-4-on of general formula I, where R represents phenyl substituted by the methyl group, nitro group by the chlorine atom, the group of dichloromethyl, tert-butyl, ethoxy, 2,2,2-trichloro-1-formamido-ethyl,(2-hydroxymetyl-4-1H-pyran-4-on-5-yl)-oxycarbonyl, R1 represents hydrogen, methyl, n, y is 0 or 1, R' represents the atom of bromine, chlorine, the group azido, hydroxy or the group of general formula NR1R2R3 where R1 to R3 is C1 to C4, the group 2,4,5-tribromimidazol-1-yl, 1-pyridyl and their salts. The substances are prepared by acylation of the compound of general formula II with the reactive derivative of acid of general formula III where R, R1, R', n and y have the abovementioned meanings.<IMAGE>

Description

Vynález sa týká derivátov 5-hydroxy-2-/hydroxymetyl/-4H-pyrán-4-onu.The present invention relates to 5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one derivatives.

Pr·; niektoré deriváty 5-hydroxy-2-/hydroxymetyl/-4H-pyrán-4-onu Ichimoto a kol. fAcj— ric, Diol. Chem., 39, 1311 (1975)} a Dobiáš a kol. [Biologia 32, 417 (1977)] uvádzajú antifungálne, antibiotické a bakteriostatické vlastnosti. Producentami 5-hydroxy-2-/hydroxyiii(:Lyl/-áll-pyrán-4-onu sú napr. kmene Aspergillus [Beelik. A., Advancos Carbohyd. Chem., 11, 145 (1950)]. Reakcie derivátov karboxylových kyselin s 5-hydroxy-2-/hydroxymetyl/-4H-pyrán-4-onav za vzniku mono. resp. diacylderívátov opisuje Beelik, A., Purves V.C.; Can. 0. Chem. 33, 1361 (1955). Nukleofilná výměna chlóru s dusíkatými nukleofilmi u 2-chlórmetyl derivátov je popísaná Ettelom (Éttel, V., Hebký, J.; Coll. Czech. Chem. Commun. 15, 35á (1950)].· Pr; some 5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one derivatives Ichimoto et al. fAcjicic, Diol. Chem., 39, 1311 (1975)} and Dobias et al. [Biologia 32, 417 (1977)] report antifungal, antibiotic and bacteriostatic properties. 5-Hydroxy-2- / hydroxy (lyl) -al-pyran-4-one producers are, for example, Aspergillus strains [Beelik. A., Advancos Carbohyd. Chem., 11, 145 (1950)]. with 5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one in the formation of mono and diacyl derivatives respectively, is described by Beelik, A., Purves VC; Can. Chem., 33, 1361 (1955). with nitrogen nucleophiles of the 2-chloromethyl derivatives is described by Ettel (Ettel, V., Hebky, J .; Coll. Czech. Chem. Commun. 15, 35a (1950)).

Predmetom vynálezu sú deriváty 5-hydroxy-2-/hydroxymetyI/-4H-pyrán-4-onu všeobecného vzorca IThe present invention provides 5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one derivatives of formula I

R -( 0 - ČH )y- /CH2/n -4CY 0 /1, kde R představuje fenyl substituovaný nezávisle metylovou skupinou, nitroskupinou alebo chlorom, skupinu dichlormetyl, terč. butyl, etoxykarbonyl, 2,2,2-trichlor-l-formamido-etyl, /2-hydroxymetyl-4-H-pyran-4-on-5-yl/-oxykarbonyl, R·^ představuje atom vodíka alebo metylové skupinu, π je 0 alebo 1, y je 0 alebo 1, R'představuje atom brómu alebo chlóru, skupinu azido, hydroxy alebo skupinu všeobecného vzorca NR^R^Rj kde R^ až R-j představuje vodík alkyl C^ až C4, skupinu 2,4,5-tribromimidazol-l-yl, 1-pyridyl a ich solii-ako hydrobromidy alebo hydrochloridy a sposob ich přípravy, ktorý spočívá v tom, že 0,9 až 1,0 molSrnych dielov zlúčeniny všeobecného vzorca IIR - (0 - CH) y - / CH 2 / n -4CY 0/1, wherein R is phenyl substituted independently with methyl, nitro, chlorine, dichloromethyl group, tert. butyl, ethoxycarbonyl, 2,2,2-trichloro-1-formamido-ethyl, (2-hydroxymethyl-4-H-pyran-4-one-5-yl) oxycarbonyl, R 6 represents a hydrogen atom or a methyl group, π is 0 or 1, y is 0 or 1, R 1 represents a bromine or chlorine atom, an azido group, a hydroxy group or a group of the formula NR 1 R 1 -R 1 wherein R 1 -R 1 represents hydrogen C 1 -C 4 alkyl, group 2, 4,5-tribromimidazol-1-yl, 1-pyridyl and their salts, such as hydrobromides or hydrochlorides, and a process for the preparation thereof comprising 0.9 to 1.0 mol parts of a compound of formula II

kde R'má vyššie uvedený význam, reaguje s 0,9 až 1,3 molárnymi dielmi reaktívneho derivátu karboxylovej kyseliny všeobecného vzorca III i1 wherein R 1 is as defined above, is reacted with 0.9 to 1.3 molar parts of a reactive carboxylic acid derivative of the formula III and III ;

R-(0 - CH) - /CH2)n - C000H /III, kde Rp Ran majú vyššie uvedený význam, ako je chlorid alebo anhydrid pri teplote -15°C až 110 °C po dobu 0,5 až 12 hodin. Ak je reaktívnym derivátom chlorid kyseliny, reakcia sa uskutočňuje s výhodou za přítomnosti bázy. V osobitnom případe sa prídavok bázy nahradí tým, že sa reakcia uskutočňuje v bázickom rozpúštadle. Zlúčeniny všeobecného vzorca I prejavujú herbicídnu a fungicídnu aktivitu, a preto je možné tieto zlúčeniny použiť ako látky pre ochranu rastlín, Zlúčeniny zasahujú do delenia rastlinných buniek a tým dochádza k chorobnému rastu nežiadúcich rastlín. Uvedené látky je možné charakterizovat ako auxinové regulátory rastu podobné ako iné deriváty fenoxyoctových kyselin.R (0 - CH) - / CH2) n - C000h / III, wherein R p Ran are as defined above, such as the chloride or anhydride at -15 DEG C. to 110 DEG C. for 0.5 to 12 hours. If the reactive derivative is an acid chloride, the reaction is preferably carried out in the presence of a base. In a particular case, the addition of the base is replaced by carrying out the reaction in a basic solvent. The compounds of formula (I) exhibit herbicidal and fungicidal activity and, therefore, can be used as plant protection agents. The compounds interfere with the division of plant cells, thereby causing the undesirable growth of plants. These compounds can be characterized as auxin growth regulators similar to other phenoxyacetic acid derivatives.

Postupy pripravy zlúčenín podía vynálezu sa obecne uskutočňujú tak, že sa k 1 molárnemu dielu derivátu 5-hydroxy-2-/hydroxymetyl/-4H-pyrán-4-ónu všeobecného vzorca II přidá 0,9 až 1,3 molárného dielu reaktívneho derivátu substituovaných kyselin všeobecného vzorca III. Ako'reaktívny derivát možno obecne použiť halogenid, najma chlorid alebo bromid, anhydrid kyseliny alebo zmesný anhydrid, alebo reaktívny ester kyseliny. V případe,The processes for the preparation of the compounds of the invention are generally carried out by adding 0.9 to 1.3 molar parts of a substituted 5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one derivative of the general formula II to a molar part of acids of formula III. The reactive derivative can generally be a halide, in particular a chloride or bromide, an acid anhydride or mixed anhydride, or a reactive acid ester. In case,

CS 272880 Bl že sa pracuje s acylhalogenidom, je výhodné použiť bázické agenty ako napr. uhličitany alkalických kovov alebo terciárně organické bázy, zvlášť je výhodné použit pyridin. Acylačná reakcia sa móže uskutočniť v bezvodom alebo vodnoorganickom prostředí. Ako bezvodé pro stredie sé vhodné ketony ako acetón alebo etylacetát. Zmkšenie komponentov reakcie váčšinou prebieha při teplote -15 °C až 50 °C s výhodou 0 °C až 5 °C. Na doreagovanie je potřebná doba 0,5 až 12 hodin. Izolácia zlúčenin sa robí známými postupmi s následnou purifikáciou, kryštalizáciou alebo chromatografiou.When working with an acyl halide, it is preferred to use basic agents such as e.g. alkali metal carbonates or tertiary organic bases, particularly preferred is pyridine. The acylation reaction can be carried out in an anhydrous or aqueous organic medium. Suitable ketones such as acetone or ethyl acetate are anhydrous to the medium. Generally, the softening of the reaction components takes place at a temperature of -15 ° C to 50 ° C, preferably 0 ° C to 5 ° C. 0.5 to 12 hours are required to react. The isolation of the compounds is carried out by known procedures followed by purification, crystallization or chromatography.

Podrobnosti jednotlivých spósobov přípravy sú uvedené v následujúcich príkladoch pre vedenia bez toho, že by sa na tieto výlučné obmedzovali.The details of the individual preparation methods are given in the following examples for the guides, without being limited to these.

Příklad 1Example 1

5-/2,2-di chlor acetoxy/-2-hydroxymetyl-4 li-pyran-4-on5- (2,2-Dichloroacetoxy) -2-hydroxymethyl-4H-pyran-4-one

Roztok 3,6 ml (0,0374 mol) chloridu kyseliny dichloroctovej v 20 ml acetonu sa přidá k 4,7 g (0,033 mol) 5-hydroxy-2-hydroxymetyl-4H-pyran-4-onu a 3,96 g (0,0374 mol) trietylaminu v 200 ml acetonu. Reakčná zmes sa mieša 12 hodin pri laboratórnej teplote, následné sa přefiltruje, rozpúšťadlo sa oddestiluje za zníženého tlaku a zvyšok sa krystalizuje z benzénu. Ziska sa 4,7 g 5-/2,2-dichloracetoxy/-2-hydroxymetyl-4H-pyran-4-on s t.t. 70 až 72 °C. XH NMR spektrum [(CD^CO] <f = 5,25 (2H, CH2-0H); 6,56 (1H, ClgCH-); 6,70 (1H, H-j); 8,06 (1H, H^).A solution of 3.6 ml (0.0374 mol) of dichloroacetic acid chloride in 20 ml of acetone was added to 4.7 g (0.033 mol) of 5-hydroxy-2-hydroxymethyl-4H-pyran-4-one and 3.96 g ( 0.0374 mol) triethylamine in 200 ml acetone. The reaction mixture is stirred at room temperature for 12 hours, then filtered, the solvent is distilled off under reduced pressure and the residue is crystallized from benzene. 4.7 g of 5- (2,2-dichloroacetoxy) -2-hydroxymethyl-4H-pyran-4-one are obtained with mp 70-72 ° C. X H NMR [(CD ^ CO] <f = 5.25 (2H, CH2 -0H), 6.56 (1 H, ClgCH-), 6.70 (1 H, Hj), 8.06 (1H, H +).

Příklad 2Example 2

5-/2-metyl-4-chlorfenoxyacetoxy/-2-[/2,4,5-tribromimidazol-l-yl/metyl] - 4-ll-pyran-4-on5- (2-methyl-4-chlorophenoxyacetoxy) -2 - [[2,4,5-tribromimidazol-1-yl] methyl] -4-11-pyran-4-one

Stupeň AGrade A

5-hydroxy-2-[/2,4,5-tribromimidazol-l-yl/metyl]-4-H-pyran-4-on5-Hydroxy-2 - [/ 2,4,5-tribromimidazol-yl / methyl] -4-H-pyran-4-one

Zmes 9,09 g 1H-2,4,5-tribromimidazolu (0,03 mol) 0,8 g hydridu sodného sa mieša pri teplote 60 °C v 50 ml dimetyl formamidu a 10 ml tetrahydrofuránu s 6,7 g (0,033 mol) 5-hydroxy-2“brommetyl-4H-pyran-4-ónu počas 12 hodin. Reakčná zmes sa následné vyleje do 500 ml 1’adovej vody a vylúčená zrazenina sa kryštalizuje z etanolu. Získá sa 9,2 g 5-hydroxy-2- [/2,4,5-tribromimidazol-l-yl/metyl] - 4-H-pyran-4-on s t.t. 205 až 207 °C . CHN = vypooi tané/nájdené: % C = 25,2, 24,75; % H = 1,18, 1,39; % N = 6,53; 6,97.A mixture of 9.09 g 1H-2,4,5-tribromimidazole (0.03 mol) 0.8 g sodium hydride is stirred at 60 ° C in 50 ml dimethyl formamide and 10 ml tetrahydrofuran with 6.7 g (0.033 mol) 5-hydroxy-2'-bromomethyl-4H-pyran-4-one for 12 hours. The reaction mixture is then poured into 500 ml of 1 N ice water and the precipitate formed is crystallized from ethanol. 9.2 g of 5-hydroxy-2- [(2,4,5-tribromimidazol-1-yl) methyl] -4-H-pyran-4-one are obtained, m.p. 205-207 ° C. CHN = calculated / found:% C = 25.2, 24.75; % H = 1.18, 1.39; % N = 6.53; 6.97.

Stupeň BGrade B

K 3,4 g produktu zo stupňa A (0,008 mol), 1,2 ml trietylamin v 100 ml acetonu sa přidá 1,54 g chloridu kyseliny 2-metyl-4-chlorfenoxyoctovej. Zmes sa zahrleva za refluxu počas 30 minút. Ro ochladení sa reakčná zmes přefiltruje, rozpúšfadlo sa oddestiluje za zníženého tlaku. Zvyšok sa kryštalizuje z benzénu. Získá sa 3,9 g 5-/2-metyl-4-chlorfenoxyacetoxy/-2-[/2,4,5-tribromimidazol-l-yl/metyl]-4-H-pyran-4-on s t.t. 130 až 133 °C. NMR | [(C3)2C0]cf = 5,31 (2H,s,CH2), 5,14(2H,s,CH2) 6,6 (lH.s.Hj) 7,3-7,05 (3H,m,Harom).To 3.4 g of the product from Step A (0.008 mol), 1.2 ml of triethylamine in 100 ml of acetone was added 1.54 g of 2-methyl-4-chlorophenoxyacetic acid chloride. The mixture was heated at reflux for 30 minutes. After cooling, the reaction mixture is filtered, and the solvent is distilled off under reduced pressure. The residue was crystallized from benzene. There were obtained 3.9 g of 5- (2-methyl-4-chlorophenoxyacetoxy) -2 - [(2,4,5-tribromimidazol-1-yl) methyl] -4-H-pyran-4-one of m.p. 133 ° C. NMR [(C 3 ) 2 CO] cf = 5.31 (2H, s, CH 2 ), 5.14 (2H, s, CH 2 ) 6.6 (1H, sH) 7.3-7.05 (3H, m, H arom).

CS 272380 BlCS 272380 Bl

Příklad 3 až 20Examples 3 to 20

Následujuce deriváty boli připravené analogicky podía příkladu 1 a sú uvedené v tab. 1.The following derivatives were prepared analogously to Example 1 and are shown in Table 1. First

bola potvrdená elementárnou analýzou a Tab. 1 was confirmed by elemental analysis and Tab. 1 spektrálnými údajmi spectral data Příklad R Example R R1 R 1 y y Π Π R' T.t. (°l R 'm.p. (L ° 3 3 C12CH-C1 2 CH- - - 0 0 0 0 N3 158N, 3 158 4 4 ci2ch-or 2 ch- - - 0 0 0 0 Br 105-107 Br 105-107 5 5 - - 0 0 0 0 OH 157-158 OH 157-158 6 6 - - 0 0 0 0 Cl 148-151 Cl 148-151 7 7 et, 0- et, 0- - - 0 0 0 0 NH2.HBr 195-198NH 2 .HBr 195-198 8 8 AS AS CH3 CH 3 1 1 0 0 OH 77-81 OH 77-81 9 9 ‘AA- 'AA- ch3 ch 3 1 1 o - about - Cl 76 Cl 76 10 10 C12CH-C1 2 CH- - - 0 0 0 0 Cl 107-109 Cl 107-109 11 11 ,_- Čff r , _- Čff r CH3 CH 3 1 1 0 0 NH2.HBr 181-183NH 2 .HBr 181-183 12 12 ΐί,φ? ΐί, φ? H H I I 0 0 NH2.HBe 197-181NH 2 .Be 197-181 13 13 H H 1 1 0 (1 0 (1 1H)3N.HC1 143-1441H) 3 N.HCl 143-144 14 14 H H 1 1 c 0 C 0 H3CH2CH2V ch3 H 3 CH 2 CH 2 In ch 3 NH 153-159 NH 153-159 .HBr .HBr 15 15 ÍCHj)3C-(CHj) 3 C- - - 0 0 0 0 HO HO 81-84 81-84 16 16 C2H5-0-CO -C 2 H 5 -O-CO - - - 0 0 0 0 OH OH 90-91 90-91 17 17 CC1-.-CH-NH-CH0 3 iCC 1 -. CH - NH - CH 3 i - - 0 0 0 0 Br br 155-157 155-157 18 18 CC1,-CH-NH-CHO i 1CC1, CH-NH-CHO and 1 - - 0 0 0- 0- |Q-HBr | Q-HBr tuhn. olej solidify. oil 19 19 H H 1 1 0 0 nh2.hcinh 2 .hci 168-170 168-170 0 0 0 0 20 B 20 B < Ar - <Ar - - - 0 0 0 0 Br br 181-183 181-183

CS 272880 8181

Příklad 21Example 21

Di-(2-hydroxymetyl-4H-pyran-4-on-5-yl )oxalátDi- (2-hydroxymethyl-4H-pyran-4-one-5-yl) oxalate

K 2,8 g 5-hydroxy-2-hydroxymetyl-4H-pyran-4-onu v 30 ml dimetylacetamidu sa přidá 1,27 g dichloridu kyseliny oxalovej při teplote 0 - 5°C. Reakčná zmes sa mieša pri uvedenej teplote 2 hodiny a následné sa vyleje do 150 ml l’adovej vody. Kryštalizáciou z etanolu vylúčeného produktu sa získá 2,9 g di-(2-hydroxymetyl-4H-pyran-4-on-5-yl)oxalát s t.t. 214 až 216 °C.To 2.8 g of 5-hydroxy-2-hydroxymethyl-4H-pyran-4-one in 30 ml of dimethylacetamide was added 1.27 g of oxalic acid dichloride at 0-5 ° C. The reaction mixture is stirred at this temperature for 2 hours and then poured into 150 ml of ice water. Crystallization from ethanol gives the product (2.9 g) di- (2-hydroxymethyl-4H-pyran-4-one-5-yl) oxalate, m.p. Mp 214-216 ° C.

Pre C14H010 (338,22) vypočítané C = 49,72 % H = 2,98 % nájdené C = 49,51 % H = 2,81 % 1H NMR spektrum (DMSO-ds)δ = 8,12 (lH.s.Hg), 6,58 (lH.s.Hj) 5,15 (2H,s,CH2).For C 14 H 10 0 treatment (338.22) calculated C = 49.72% H = 2.98% found C = 49.51% H = 2.81% 1 H NMR (DMSO-d) δ = 8 , 12 (lH.s.Hg), 6.58 (lH.s.Hj) 5.15 (2H, s, CH2).

Příklad 22Example 22

5-(2,2-dichloracetoxy)-2-azidometyl-4H-pyran-4-on5- (2,2-dichloroacetoxy) -2-azidomethyl-4 H -pyran-4-one

K roztoku 3,2 g 5-(2,2-dichloracetoxy)-2-brom-inetyl-4H-pyran-4-onu v 40 ml dimetylformamidu sa přidá 0,7 g azidu sodného. Reakčná zines sa inieša pri teplote 15 °C počas 5 hodin a následné sa vyleje do 400 ml vody. Vylúčený produkt sa odfiltruje a kryštalizuje z benzenu. Získá sa 2,1 g 5-(2,2-dichloracetoxy)-2-azidometyl-4H-pyran-4-onu s t.t. 158 °C.To a solution of 3.2 g of 5- (2,2-dichloroacetoxy) -2-bromo-ethyl-4H-pyran-4-one in 40 ml of dimethylformamide was added 0.7 g of sodium azide. The reaction zines were stirred at 15 ° C for 5 hours and then poured into 400 ml of water. The precipitated product is filtered off and crystallized from benzene. 2.1 g of 5- (2,2-dichloroacetoxy) -2-azidomethyl-4H-pyran-4-one of m.p. 158 ° C.

1h NMR spektrum [(CD2)2C0j <Λ 5,1 (2H,s,CH2Cl) 6,59 (1H,s,C12CH-) 6,70 (1H,s,H-j) 0,06 (1H,s,H6) 1 H NMR Spectrum [(CD 2 ) 2 CO 3 Λ 5.1 (2H, s, CH 2 Cl) 6.59 (1H, s, C 12 CH-) 6.70 (1H, s, H 3) O, 06 (1 H, s, H 6 )

Příklad 23Example 23

5-(2,2-dichloracetoxy)-2-aminometyl-4H-pyran-4-on hydro bromid5- (2,2-dichloroacetoxy) -2-aminomethyl-4H-pyran-4-one hydrobromide

K 2,8 g (0,01 mol) produktu z příkladu 22 v 50 ml benzenu sa přidá 1,4 g (0,015 mol) fenolua 50 ml kyseliny octovoj, a za refluxu sa do zmesi fúka suchý bromovodík počas 1 hodiny. Reakčná zmes sa ochladí na 10 °C a nechá stát' 1 hodinu. Vylúčený produkt sa krystalizuje 2 krát zo zmesy metanol éter. Získá sa 1,15 g 5-/2,2-dichloracetoxy/-2-aminometyl-4H-pyran-4-on hydrobromid s t.t. 218 až 222 °C.To 2.8 g (0.01 mol) of the product of Example 22 in 50 ml of benzene was added 1.4 g (0.015 mol) of phenol and 50 ml of acetic acid, and dry hydrogen bromide was blown into the mixture at reflux for 1 hour. The reaction mixture was cooled to 10 ° C and allowed to stand for 1 hour. The precipitated product was crystallized 2 times from methanol ether. 1.15 g of 5- (2,2-dichloroacetoxy) -2-aminomethyl-4H-pyran-4-one hydrobromide, m.p. Mp 218-222 ° C.

NMR spektrum (dimetylsulfoxid-d^) = 6,52 (lH,s,CH) 6,68 (1H,s,Hj) 8,22 (lH,s,Hg) 8,65 (4H,bs,0H,NH2).NMR Spectrum (dimethylsulfoxide-d6) = 6.52 (1H, s, CH) 6.68 (1H, s, Hj) 8.22 (1H, s, Hg) 8.65 (4H, bs, 0H, NH) 2 ).

Claims (2)

1. Deriváty 5-hydroxy-2-/hydroxymetyl/-4H-pyrán-4-onu všeobecného vzorca kde R představuje fenyl substituovaný nezávisle netylovou skupinou alebo cblórom, skupinu dichlormetyl, terč. butyl, etoxykarbonyl, 2,2,2-trichlor-l-formamido-etyl, /2-hydraxymetyl-4K-pyran-4-on-5-yl/-oxykarbonyl, R^ představuje atom vodíka alebo metylová skupinu, n je 0 alebo 1 a R' představuje atom brómu alebo chlóru, skupinu 2,4,5-tribromimidazol-l-yl, 1-pyridyl, skupina azido, hydroxy alebo skupinu všeobecného vzorca NR^Rj kde R^ až R-j představuje vodík, alkyl C^ až C^ a ich soli ako hydrobromidy ale bo hydrochloridy.A compound of the formula wherein R is phenyl substituted independently with a methyl or chloro group, a dichloromethyl group, a tert-butylamino group, or a 5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one derivative. butyl, ethoxycarbonyl, 2,2,2-trichloro-1-formamido-ethyl, [2-hydroxymethyl-4K-pyran-4-one-5-yl] oxycarbonyl, R1 is hydrogen or methyl, n is 0 or 1 and R 'represents a bromine or chlorine atom, a 2,4,5-tribromimidazol-1-yl, 1-pyridyl, azido, hydroxy group or a group represented by the formula NR 1 -R 1 wherein R 1 -R 1 is hydrogen, C 1-6 alkyl to C12 and their salts as hydrobromides or hydrochlorides. 2. Spósob pripravy derivátov podlá bodu 1, vyznačujúci sa tým, že 0,9 až 1 molárnych dielov zlúčeniny všeobecného vzorca II H° 711 ’ kde R' má vyššie uvedený význam, reaguje s 0,9 až 1,3 molárnymi dielmi reaktívneho derivátu kyseliny všeobecného vzorca III R12. A process for the preparation of derivatives according to claim 1, characterized in that 0.9 to 1 molar parts of the compound of formula II H ° 711 'wherein R' is as defined above, is reacted with 0.9 to 1.3 molar parts of the reactive derivative. of an acid of formula III R 1 R -(0 -CH) -/CH2/n - C02H /III, kde R|, Ran majú vyššie uvedený význam, ako je chlorid alebo anhydrid pri teplote -15 °C až 110 °C po dobu 0,5 až 12 hodin.R - (O-CH) - / CH 2 / n - CO 2 H / III, wherein R 1, Ran are as defined above, such as chloride or anhydride at -15 ° C to 110 ° C for 0.5 up to 12 hours.
CS47789A 1989-01-25 1989-01-25 Derivatives of 5-hydroxy-2 (hydroxymethyl)-4h-pyran-4-on and method of their preparation CS272880B1 (en)

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