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 PDFInfo
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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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- BEJNERDRQOWKJM-UHFFFAOYSA-N kojic acid Chemical class OCC1=CC(=O)C(O)=CO1 BEJNERDRQOWKJM-UHFFFAOYSA-N 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 5
- -1 ethoxy, 2,2,2-trichloro-1-formamido-ethyl Chemical group 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical class Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims description 2
- 150000003840 hydrochlorides Chemical class 0.000 claims description 2
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000006318 tert-butyl amino group Chemical group [H]N(*)C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000000460 chlorine Substances 0.000 abstract description 5
- 238000005917 acylation reaction Methods 0.000 abstract description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- 230000010933 acylation Effects 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 abstract 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 229960004705 kojic acid Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- ABYSGRXBGLVRGO-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetyl chloride Chemical compound CC1=CC(Cl)=CC=C1OCC(Cl)=O ABYSGRXBGLVRGO-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- 229930192334 Auxin Natural products 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000002363 auxin Substances 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- FBCCMZVIWNDFMO-UHFFFAOYSA-N dichloroacetyl chloride Chemical compound ClC(Cl)C(Cl)=O FBCCMZVIWNDFMO-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MDKXBBPLEGPIRI-UHFFFAOYSA-N ethoxyethane;methanol Chemical compound OC.CCOCC MDKXBBPLEGPIRI-UHFFFAOYSA-N 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WZNJWVWKTVETCG-UHFFFAOYSA-N kojic acid Natural products OC(=O)C(N)CN1C=CC(=O)C(O)=C1 WZNJWVWKTVETCG-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- HVZWVEKIQMJYIK-UHFFFAOYSA-N nitryl chloride Chemical compound [O-][N+](Cl)=O HVZWVEKIQMJYIK-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical class OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
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
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 C14Hlé010 (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 ).
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