CS239396B1 - 2-Acyloxyethylisothiocyanates and methods for their preparation - Google Patents
2-Acyloxyethylisothiocyanates and methods for their preparation Download PDFInfo
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- CS239396B1 CS239396B1 CS845310A CS531084A CS239396B1 CS 239396 B1 CS239396 B1 CS 239396B1 CS 845310 A CS845310 A CS 845310A CS 531084 A CS531084 A CS 531084A CS 239396 B1 CS239396 B1 CS 239396B1
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Abstract
Vynález opisuje jednostupňovú syntézu 2-acyloxyetylizotiokyanátov reakciou tiofos- génu s A2-oxazolínmi v prostředí organického vodou sa nemiešajúceho rozpúšťadla v přítomnosti bázických činidiel v rozmedzí teplot 0—30 °C. Látky sa vyznačujú vysokou účinnosťou voči kvasinkám a pliesňain.The present invention provides a single-step synthesis of 2-acyloxyethylisothiocyanates by reacting a thiophosgene with A2-oxazoline in an organic water-immiscible solvent medium in the presence of basic reagents in the range of 0-30 ° C. The substances are characterized by high efficacy against yeast and fungus.
Description
239396
Vynález sa týká 2-acyloxyetylizotiokyaná-tov obecného vzorca I
R
kde R1 značí vodík, metyl, etyl, propyl, izopro-pyl, fenyl alebo benzyla R2 značí vodík metyl. Látky a sposob ich přípravy podía vyná-lezu nie sú doteraz v literatúre opísané.
Podstata sposobu přípravy lótok podía vy-nálezu spočívá v tom, že A2-oxazolíny obec-ného vzorca II
kde R1 a R2 značí to isté ako vo vzorci I reagu-jú s tiofosgénom v prostředí organického svodou sa nemiešajúcelio rozpúšťadla, výhod-né v chloroforme, 1,2-dichlóretáne alebometylénchloride, za přítomnosti vody a bá-zických činidiel ako uhličitan vápenatý, u-hličitan barnatý, uhličitan sodný v rozmedzíteplot 0 až 30 °C. Výhoda sposobu přípravy látok podía vy-nálezu spočívá v tom, že syntézy sú jedno-stupňové a získavajú sa produkty v dobrýchvýťažkoch a čistotě. V ďalšom je předmětný vynález objasněnýv príkladoch prevedenia, hoci sa na tietovůbec neobmedzuje. Příklad 1
Prípraýa 2-benzoyloxyetylizotiokyanátu K suspenzii 8 g uhličitanu vápenatého v60 ml vody a 5,75 g tiofosgénu v 50 ml chlo-roformu sa za intenzívneho miešania pri-kvapkáva 7,35 g 2-fenyl-A2-oxazolínu v 30 mlchloroformu pri 0—5 °C v priebehu 15 mi-nút. Po přidaní celého množstva 2-fenyl-A2--oxazolínu sa reakčná zmes vyberie z chla-diaceho kúpeía a mieša sa ešte 3 h pri la-boratórnej teplote. Chloroformová vrstva sapotom oddělí, vysuší síranom horečnatým achloroform sa oddestiluje. Zvyšok sa čis-tí frakčnou destiláciou vo vákuu. 2-Benzoyl-oxyetylizotiokyanát destiluje pri 122—124 °Ca tlaku 1,3 kPa. Příklad 2 Příprava 2-acetyloxyetylizotiokyanátu K suspenzii 10 g uhličitanu bárnatého v100 ml vody a 11,5 g tiofosgénu v 50 mldichlórmetánu sa za intenzívneho miešaniapri laboratórnej teplote prikvapkáva 8,5 g2-metyl-A2-oxazolínu v 50 ml dichlórmetánuv priebehu 30 minut. Po dvoch hodináchmiešania sa oddělená chloroformová vrstvavysuší bezvodým chloridom vápenatým aprodukt sa získá frakčnou destiláciou pri59—61 °C/1,3 kPa. Příklad 3 Příprava l,l-dimctyl-2-propionyloxyetylizo-tiokyanátu K 5,75 g tiofosgénu v 40 ml 1,2-dichlór-etánu sa za miešania prikvapkáva 6,36 g2-etyl-4,4-dimetyloxazolínu v 20 ml 1,2-di-chlóretánu. Získaný roztok sa v priebehu10 minut přidá k intenzívně miešanej sus-penzii 12 g uhličitanu vápenatého v 80 mlvody pri labaratórnej teplote. Po troch ho-dinách miešania sa vrstva 1,2-dichlóretánuoddělí, vysuší bezvodým chloridom vápena-tým a 1,2-dichlóretán sa oddestiluje. Zvy-šok sa přečistí vákuovou destiláciou. 1,1-Di-metyl-2-propionyloxyetylizotiokyanát desti-luje pri 62—64 °C/0,2 kPa. Příklad 4 K 5,75 g tiofosgénu v 30 ml chloroformusa za miešania prikvapká 9,46 g 2-benzyl--4,4-dimetyloxazolínu v 30 ml chloroformu.Získaný chloroformový roztok sa v priebe-hu 15 minut přidá k intenzívně miešanej sus-penzii 15 g uhličitanu bárnatého v 100 mlvody pri laboratórnej teplote. Po štyrochhodinách miešania sa chloroformová vrstvaoddělí, vysuší bezvodým chloridom vápena-;tým a produkt sa získá frakčnou destilá-ciou pri 105—110 °C a tlaku 0,2 kPa.
Fyzikálno-chemické vlastnosti a elemen-tárně analýzy látok podía vynálezu sú uve-dené v tabuíke 1.
Hodnoty antimikrobiálnej účinnosti látokvzorca*! sú uvedené v tabuíke 2.
Antibakteriálna účinnost bola posudzo-vaná na kultúrach Bacillus subtilis, Staphy-lococus aureus, Próteus vulgaris. K bakte-riálně j suspenzii v bujóne (OD g7g™m = 0,25)
boli přidané roztoky izotiokyanátov v di-metylsulfoxide tak, že výsledná koncentrá-cia izotiokyanátov kolísala v rozpátí 1.10_G
Važ 1.10”3 mol dm-3. Koncentrácia dimetyl-sulf oxidu reprezentovala 1 %.
Baktérie boli 48 hodin staticky inkubova-né pri 37 °C, pričom bol v 12 hodinovýchintervaloch sledovaný. denzitometrický rast. 239396 5 6
Na základe spektrofotometrických údajovbola určená minimálna inhibičná koncen-trácia MIC, číže najmenšia koncentrácia in-hibítora, ktorá ešte úplné zabrzdila rast.
Protikvasinková účinnost' bola analogickysledovaná na Candida albicans a Saccharo-myces cerevisiae až na to, že ako kultivač-ně médium slúžila syntetická podá Vita[Hroncová M., Drobnica E.: Induction of my-celial type of development in Candida albi-cans by low glucose concentration, Mycopa-thologia 76, 83—86 (1981)] a rast bol sle- dovaný pri 28 °C 48 hodin. Inhibitor bol při-dávaný k suspenzii kvasiniek o OD | ™ == 0,15.
Sposob charakterizácie antifungálnej ú-činnosti (Aspergillus niger) je opísaný vpráci Drobnica E. a kol.: Antifungal activityof isoťhiocyanates and rélated compounds.,Appl. Microbiol. 13, 701—709 (1967). Kulti-vácia sa uskutočňovala staticky v Czapek--Doxovom médiu pri 28 °C počas 48 hodin, 239396 TTt^’7lSCODCO1HCO0^c^C303 CM0303φ_ lfl ° °°r oo oo^ o, ó/co ιό" ιό" cm" r-Γ co co cm" cm" [>." t< irf co"io" co" o" 03"ΗγΗ^ΝΗΗτΗΗΗΗΗγΗΗΗΝγΗ o txo M4
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co 1Ό Φ r-4, 00 co coCO ΙΌ í> 1Ό CO" CO" CO 00
oO CO Ή O Φ co co o 03 rd Φ O φ Λ (—1 73 03 CO CO co Φ ΙΌ co CD θ' CD ΙΌ 1Ό ΙΌ 1Ό CD Οι u xF ’φ" φ" ιό" co" co" co" co" I>." t< l> ιό" ΙΌ *cn cO >> > c o řM cO CO D! 03 □3 co co co co CM Φ r-l CM O CO O Φ CM 03 ΙΌ Q co <o in^ Φ o !O CO^ Φ IS CO' IS' co CO' Ol C3 l< co" rH i—i co" oo" cm" cm" rd t—1 co" co" co" co" 1Ό ιό" C/3 03 CO ΙΌ ΙΌ Φ Φ Φ Φ CD co ΙΌ 1Ό 1Ό ΙΌ ΙΌ 1Ό Φ Φ CO
O O CO O O O ΙΌ O O ΙΌ ΙΌ O O 1Ό O O CM o co O ’φ CO CO £> CO co co CO t> tH >> rH 1> O t> O l>. O O o o rH CM rH CM rH CM rH CM rH CM t-H CM rH CM tH CM 73 c
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Tabulka 1
Fyzikálno-chemické vlastnosti a elementárne analýzy látok všeobecného vzorca CJ —V03 fĎ f-l O ·N § ca ca cm cm
4x1CO CMrH CD
O O o ,>NCO £ *" >
CO
OJ
•rH tí 03 >o a
r—I
N « w. w2^0772^° C/5 (Z)
CO s Γn°w2 nO cm-¾^ 2 in co ή κ Λ jh
HH O l;? Φ Z5 t>> Φ Φ «-1 CO TT o tH O %CVJ ΕΗ«τηΪΜΤΗ"Μ^Ν _1 · *Λ ' l-~ —* ČO '——1’ (ΎΊ 05)'-—' Oi'“ Φ
CM
CM
CM
O ιό
E
CO
CJ (75 t cq í—i O CM,2 σ>"®ΊΌE Ή cO'—/
O
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O S-i
CM | | | | | | 1 o o O O O O ' Ογ—ίΓΗτΗτ—ΙτΗνίΟ OOrflrHWCOCOΛ CO" t< ΙΌ CO" CO" CO" a Λ A Λ Λ A A Λ co
CO in 03 ΙΌ
CM ΙΌ ΙΌ
O
* Φ * co * 03 * ID 4» 0 03 CO 03 03 t ΙΌ | Λ '03 '03 M 1 | 1 1 tí CM ϊ> co Φ C3 <0 CO 03 03 1Ό 03 o CQ co Φ o co 03
CO ιό ΙΌ 00 co o ΙΌ
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E
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Hodnoty MIC sú uvádzané v mol.
239396
The present invention relates to 2-acyloxyethylisothiocyanates of the formula I
R
wherein R 1 is hydrogen, methyl, ethyl, propyl, isopropyl, phenyl or benzyl R 2 is hydrogen methyl. The compounds and methods for their preparation according to the invention are not yet described in the literature.
The essence of the method of preparation of the compositions according to the invention is that the A2-oxazolines of the general formula II
wherein R 1 and R 2 are the same as in Formula I, reacting with thiophosgene in an organic effluent, non-mixed solvents, preferably in chloroform, 1,2-dichloroethane or methylene chloride, in the presence of water and alkaline agents such as calcium carbonate, barium carbonate, sodium carbonate in the range of 0 to 30 ° C. The advantage of the process of preparing the compounds of the invention is that the syntheses are single-stage and the products are obtained in good yields and purity. In the following, the present invention will be elucidated in the examples, although it is not limited thereto. Example 1
Preparation of 2-benzoyloxyethylisothiocyanate To a suspension of 8 g of calcium carbonate in 60 ml of water and 5.75 g of thiophosgene in 50 ml of chloroform, 7.35 g of 2-phenyl-A2-oxazoline in 30 ml of chloroform at 0-5 are added dropwise with vigorous stirring. ° C over 15 minutes. After addition of the entire amount of 2-phenyl-A2-oxazoline, the reaction mixture is removed from the cooling bath and stirred for a further 3 hours at room temperature. The chloroform layer was separated, dried over magnesium sulfate, and the chloroform was distilled off. The residue is purified by fractional distillation under vacuum. 2-Benzoxy-oxyethyl isothiocyanate distils at 122-124 ° C and 1.3 kPa. Example 2 Preparation of 2-acetyloxyethylisothiocyanate To a suspension of 10 g of barium carbonate in 100 ml of water and 11.5 g of thiophosgene in 50 ml of dichloromethane, 8.5 g of 2-methyl-A2-oxazoline in 50 ml of dichloromethane are added dropwise over 30 minutes. After two hours of stirring, the separated chloroform layer was dried over anhydrous calcium chloride and the product was obtained by fractional distillation at 59-61 ° C / 1.3 kPa. Example 3 Preparation of 1,1-dimethyl-2-propionyloxyethylisothiocyanate To 5.75 g of thiophosgene in 40 ml of 1,2-dichloroethane, 6.36 g of 2-ethyl-4,4-dimethyloxazoline in 20 ml of 1 are added dropwise. , 2-dichloroethane. The resulting solution is added over a period of 10 minutes to a vigorously stirred suspension of 12 g of calcium carbonate in 80 ml of water at labarate temperature. After stirring for three hours, the 1,2-dichloroethane layer was separated, dried over anhydrous calcium chloride, and 1,2-dichloroethane was distilled off. The residue is purified by vacuum distillation. 1,1-dimethyl-2-propionyloxyethylisothiocyanate distils at 62-64 ° C / 0.2 kPa. EXAMPLE 4 9.46 g of 2-benzyl-4,4-dimethyloxazoline in 30 ml of chloroform are added dropwise to 5.75 g of thiophosgene in 30 ml of chloroform, with stirring. The resulting chloroform solution is added to the vigorously stirred suspension over a period of 15 minutes. 15 g of barium carbonate in 100 ml of water at room temperature. After stirring for four hours, the chloroform layer was separated, dried over anhydrous calcium chloride, and the product was obtained by fractional distillation at 105-110 ° C and 0.2 kPa.
Physico-chemical properties and elemental analysis of the compounds of the invention are shown in Table 1.
Antimicrobial efficacy values of the formula *! are listed in Table 2.
The antibacterial activity was assessed in cultures of Bacillus subtilis, Staphylococcus aureus, Proteus vulgaris. For bacterial suspension in broth (OD g7g ™ m = 0.25)
isothiocyanate solutions in dimethyl sulfoxide were added such that the resulting isothiocyanate concentration varied at 1.10 g
To 1.10 ”3 mol dm-3. The dimethylsulfoxide concentration represented 1%.
Bacteria were statically incubated at 37 ° C for 48 hours, followed by 12 hours. densitometric growth. 239396 5 6
Based on spectrophotometric data, the minimum inhibitory concentration of MIC was determined, decreasing the smallest concentration of inhibitor that still fully inhibited growth.
The anti-yeast activity was analogous to Candida albicans and Saccharomyces cerevisiae, except that the synthetic medium was Vita [Hroncová M., Drobnica E .: Induction of my-celial type of development in Candida albi-cans by low glucose concentration, Mycophorology 76, 83-86 (1981)] and growth was monitored at 28 ° C for 48 hours. The inhibitor was added to the yeast suspension of OD ™ = 0.15.
The method for characterizing antifungal activity (Aspergillus niger) is described in Drobnica E. et al., Antifungal activity, isohiocyanates and rélated compounds., Appl. Microbiol. 13, 701-709 (1967). The cultivation was performed statically in Czapek-Dox medium at 28 ° C for 48 hours, 239396 TTt ^ '7lSCODCO1HCO0 ^ c ^ C303 CM0303φ_fl ° °° r o oo, o / co ιό "cm" r -Γ what about cm "cm"[>." t <irf co "io" co "o" 03 "ΗγΗ ^ ΝΗΗτΗΗΗΗΗγΗΗΗΝγΗ o txo M4
II Ό3 and ω
4-J 73 ι-Η
N '03 and ca + - ·
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co 1 Φ r-4, 00 what coCO ΙΌ í> 1Ό CO "CO" CO 00
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OO CO OOO ΙΌ OO ΙΌ O OO 1Ό OO CM co 'φ £ CO £> CO CO co co co H H H H H H H H OO oo rH CM r CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM
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Table 1
Physico-chemical properties and elemental analyzes of compounds of general formula CJ - V03 fĎ fl O · N § ca ca cm cm
4x1CO CMrH CD
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WHAT
OJ
• rH ti 03> oa
r — I
N «w. w2 ^ 0772 ^ ° C / 5 (W)
CO s Γn ° w2 nO cm-¾ ^ 2 in what κ jh
HH O 1; 5 Z5 t >> Φ Φ -1 -1 tH O CO Η Η TT TT o Ν Ν Ν Ν Ν Ν 1 1 1 1 1 1 1 1 1 Ν Ν Ν Ν 1 Ν 1 1 1 “
CM
CM
CM
O ιό
E
WHAT
CJ (75 t q i, CM, 2 σ>"ΊΌ Ή O O O 2 / - /
O
CM
WHAT
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H fl
CO óo 3> 73 3 03 + ->
O Si
CM | | | | | | 1 oo OOOO Ογ — ίΓΗτΗτ — ΙτΗνίΟ OOrflrHWCOCOΛ CO "t <ΙΌ CO" CO "CO" and Λ A Λ Λ AA Λ co
CO in 03 ΙΌ
CM ΙΌ ΙΌ
O
* Φ * co * 03 * ID 4 »0 03 CO 03 03 | 03 '03 '03 M 1 | 1 1 t CM CM ϊ> co Φ C3 <0 CO 03 03 1Ό 03 o CQ co Φ o co 03
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'WHAT
4 - »
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Sj (K * M * ^ iii)
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E u
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N'03 £
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MIC values are reported in moles.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS845310A CS239396B1 (en) | 1984-07-09 | 1984-07-09 | 2-Acyloxyethylisothiocyanates and methods for their preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS845310A CS239396B1 (en) | 1984-07-09 | 1984-07-09 | 2-Acyloxyethylisothiocyanates and methods for their preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS531084A1 CS531084A1 (en) | 1985-05-15 |
| CS239396B1 true CS239396B1 (en) | 1986-01-16 |
Family
ID=5397762
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS845310A CS239396B1 (en) | 1984-07-09 | 1984-07-09 | 2-Acyloxyethylisothiocyanates and methods for their preparation |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS239396B1 (en) |
-
1984
- 1984-07-09 CS CS845310A patent/CS239396B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS531084A1 (en) | 1985-05-15 |
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