CS271126B1 - 1-(4-/4-/2-tetrahydropyranyloxy/butoxy/phenyl/alkyl ester of 3-/2,2-dihalogenethenyl/-2,2-dimethylcyclopropancarboxyl acid as biologically active substance and method of its preparation - Google Patents
1-(4-/4-/2-tetrahydropyranyloxy/butoxy/phenyl/alkyl ester of 3-/2,2-dihalogenethenyl/-2,2-dimethylcyclopropancarboxyl acid as biologically active substance and method of its preparation Download PDFInfo
- Publication number
- CS271126B1 CS271126B1 CS884202A CS420288A CS271126B1 CS 271126 B1 CS271126 B1 CS 271126B1 CS 884202 A CS884202 A CS 884202A CS 420288 A CS420288 A CS 420288A CS 271126 B1 CS271126 B1 CS 271126B1
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- CS
- Czechoslovakia
- Prior art keywords
- phenyl
- butoxy
- tetrahydropyranyloxy
- dihalogenethenyl
- preparation
- Prior art date
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 229940088623 biologically active substance Drugs 0.000 title claims abstract 3
- 238000000034 method Methods 0.000 title claims description 4
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 title description 3
- 239000002253 acid Substances 0.000 title 1
- 125000003884 phenylalkyl group Chemical group 0.000 title 1
- -1 hydroxyl compound Chemical class 0.000 claims abstract description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000007524 organic acids Chemical class 0.000 claims abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 241000238876 Acari Species 0.000 abstract 1
- 241000238631 Hexapoda Species 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 230000000361 pesticidal effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LLMLSUSAKZVFOA-UHFFFAOYSA-N 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(O)=O LLMLSUSAKZVFOA-UHFFFAOYSA-N 0.000 description 1
- ZDHSRKKHIONHIH-UHFFFAOYSA-N 3-(6,6-dichlorocyclohexa-2,4-dien-1-yl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound OC(=O)C1C(C)(C)C1C1C(Cl)(Cl)C=CC=C1 ZDHSRKKHIONHIH-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- 241000895647 Varroa Species 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
Vynález ee týká l-^4-[4-(2-tetrahydropyranyloxy)butoxy]fenyl]alkylesteru 3-(2,2-dihalogenethenyl)-2,2-dimethylcyklopropankarboxylové kyseliny jako biologicky účinné látky a způsobu její přípravy.The invention relates to 3- (2,2-dihalogenethenyl) -2,2-dimethylcyclopropanecarboxylic acid 1- [4- (4- (2-tetrahydropyranyloxy) butoxy) phenyl] alkyl ester as a biologically active agent and a process for its preparation.
Podstatou vynálezu je l-^4-[4-(2-tetrahydropyranyloxy)butoxy]fenyl}alkyleater 3-(2,2-dihalogenethenyl)-2,2-dimethylcyklopropankarboxylové kyseliny obecného vzorce IThe present invention relates to 3- (2,2-dihalogenethenyl) -2,2-dimethylcyclopropanecarboxylic acid 1- [4- (2-tetrahydropyranyloxy) butoxy] phenyl} alkyl ester of the formula I
CH(R)OCOCH-CH -CH-CXO \/ XCH (R) OCOCH-CH-CH-CX O / X
C(CH3)2 (I).C (CH 3 ) 2 (I).
kde symbol R značí alkylskupinu s rovným či rozvětveným řetězcem s maximálně 4 atomy uhlíku, symbol X značí halogen (chlor, brom).wherein R is straight or branched chain alkyl of up to 4 carbon atoms, X is halogen (chlorine, bromine).
Způsob přípravy l-(4-[4-(2-tetrahydropyranyloxy)butoxy]fenyl]alkylesteru 3-(2,2dihalogenethenyl)-2,2-dimethylcyklopropankarboxylové kyseliny obecného vzorce I ae vyznačuje tím, že se nechá reagovat hydroxyslouČenina obecného vzorce II •CH(OH)R (II), kde symbol R má výše uvedený význam a organickou kyselinou obecného vzorce IIIA process for the preparation of 3- (2,2-dihalogenethenyl) -2,2-dimethylcyclopropanecarboxylic acid 1- (4- [4- (2-tetrahydropyranyloxy) butoxy] phenyl) alkyl ester of formula (I) and characterized in that the hydroxy compound of formula (II) is reacted. CH (OH) R (II) wherein R is as defined above and an organic acid of formula III
XoC-CH-CH-CH-C00H 2 \/X o C-CH-CH-CH-C00H 2 \
C(CH3)2 (III), kde aymbol X má výše uvedený význam za přítomností katalytického množství 4-dimethylaminopyridinu a ekvimolárního množství dicyklohexylkarbodiimidu při teplote 10 aŽ 20 °C nebo s chloridem či anhydridem organické kyseliny za přítomnosti ekvimolárního množství bezvodého pyridinu při 20 až °cC (CH 3 ) 2 (III) wherein aymbol X is as defined above in the presence of a catalytic amount of 4-dimethylaminopyridine and an equimolar amount of dicyclohexylcarbodiimide at 10-20 ° C or with an organic acid chloride or anhydride in the presence of an equimolar amount of anhydrous pyridine at 20 to ° C
V dalším je vynález blíže objasněn na příkladu provedení, aniž se na tento výlučně omezuje.In the following, the invention is explained in more detail by way of example without being limited thereto.
PříkladExample
0,2 g(l mmol) 3-(2,2-dichloretheny1)-2,2-dimethylcyklopropankarboxylové kyseliny, 0,33 g (1,1 mmol) l-{4£4-(2-tetrahydropyranyloxy)butoxyJfenyl}-1-propanolu, 0,2 g (1 mmol) dicyklohexylkarbodiimidu a 0,01 g (0,1 mmol) Ν,Ν-dimethylaminopyridinu bylo mícháno v 10 ml bezvodého diethyléteru při 15 až 20 °C po dobu 2 hodin. Po zředění reakční směsi diethyléterem, filtrací a promytí postupně 5%ním roztokem kyseliny chlorovodíkové a vodou byla éterická vrstva vysušena nad bezvodým síranem sodným a odpařena. Odparek, děleny sloupcovou chromátografií na silikagelu s 8 hmot. % vody (eluční činidlo petroléter obsahující až 20 obj. % diethyléteru) poskytl 0,26 g (52 %) l-£4-[4-(2-tetrahydropyranýloxy)butoxy]feny1Jpropylesteru 3-(2,2-dichloretheny1)-2,2-dimethy1cyklopropankarboxylové kyseliny.0.2 g (1 mmol) of 3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid, 0.33 g (1.1 mmol) of 1- {4- [4- (2-tetrahydropyranyloxy) butoxy] phenyl} - 1-propanol, 0.2 g (1 mmol) of dicyclohexylcarbodiimide and 0.01 g (0.1 mmol) of Ν, Ν-dimethylaminopyridine were stirred in 10 ml of anhydrous diethyl ether at 15-20 ° C for 2 hours. After diluting the reaction mixture with diethyl ether, filtering and washing successively with 5% hydrochloric acid solution and water, the ether layer was dried over anhydrous sodium sulfate and evaporated. The residue was separated by column chromatography on silica gel with 8 wt. % water (eluent petroleum ether containing up to 20 vol% diethyl ether) gave 0.26 g (52%) of 1- (4- (2-tetrahydropyranyloxy) butoxy] phenyl) propyl ester of 3- (2,2-dichloroethenyl) -2 2-dimethylcyclopropanecarboxylic acid.
IČ analýza (CC14,5%): 1725,171С(|‘С»0 ester. ) ,1614..1586,1516(,'arom. ), 1614 , (i^C-C konj.), 1389,1378,137O(J'BCH,)cm“1.IR analysis (CCl 4 , 5%): 1725, 1717C (| C? O ester.), 1614..1586, 1516 (,? Arom.), 1614, (? CC conj.), 1389, 1378, 137O (J ' B CH) cm -1 .
NMR analýza (13C, CDClp 200KHz): 10. OO(CH3CH2O) , 15.09,28. 41/(011^) 2C/, 19.54 (CH^HjO-^^ ),NMR analysis ( 13 C, CDCl 3 200KHz): 10 O (CH 3 CH 2 O), 15.09.28. 41 / (011)) 2 C, 19.54 (CH 2 H 2 O 2 -).
25.35(CH2CH20),26.24,26.36(CH2CH2C-C),27.42/t>-C(CH3)2/,29.17(CH2CH3),25.35 (CH 2 CH 2 O), 26.24,26.36 (CH 2 CH 2 CC), 27.42 / t> -C (CH 3 ) 2 /.29.17 ( CH 2 CH 3 ),
30.74(CH2CTq),32.19,32.34(CH-CH),62.33(CH2-0-CH-0),67.69(CH2OCH-O)77. 26(CH0),30.74 (CH 2 CTq), 32.19, 32.34 (CH-CH), 62.33 (CH 2 -O-CH-O), 67.69 (CH 2 OCH-O) 77. 26 (CH0)
98.85(CHq),12O,51(CC12),125.03(CH=),114.33,127.92,142.29,158.72(arom. C).98.85 (CHQ), 12o, 51 (CC1 2), 125.03 (CH =), 114.33,127.92,142.29,158.72 (arom. C).
Biologické účinky byly zkoušeny na roztoči Varroa jacobaoni. Pro l-^4-[4~(2-tetraby dropy raný 1 oxy )but oxy]fenyl]propylester 3-(2,2-dichlorethenyl)-2,2-dimethylcyklopropankarboxylové kyseliny (kličková kontaktní aplikace, l%ní vodná emulse) byla nalezena během 24 hodin 97%ní akaricidní účinnost. Dále byla zkoušena biologická účinnost na roztoči Tetranychus urticae.Biological effects were tested on the Varroa jacobaoni mite. For 3- (2,2-dichloro-phenyl) -2,2-dimethyl-cyclopropanecarboxylic acid 1- [4- (2-tetrahydro-1-oxo-butoxy) -phenyl] -propyl ester (loop contact application, 1% aqueous emulsion) ) was found to have 97% acaricidal activity within 24 hours. In addition, the biological activity of Tetranychus urticae was tested.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS884202A CS271126B1 (en) | 1988-06-16 | 1988-06-16 | 1-(4-/4-/2-tetrahydropyranyloxy/butoxy/phenyl/alkyl ester of 3-/2,2-dihalogenethenyl/-2,2-dimethylcyclopropancarboxyl acid as biologically active substance and method of its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS884202A CS271126B1 (en) | 1988-06-16 | 1988-06-16 | 1-(4-/4-/2-tetrahydropyranyloxy/butoxy/phenyl/alkyl ester of 3-/2,2-dihalogenethenyl/-2,2-dimethylcyclopropancarboxyl acid as biologically active substance and method of its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS420288A1 CS420288A1 (en) | 1990-01-12 |
| CS271126B1 true CS271126B1 (en) | 1990-08-14 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS884202A CS271126B1 (en) | 1988-06-16 | 1988-06-16 | 1-(4-/4-/2-tetrahydropyranyloxy/butoxy/phenyl/alkyl ester of 3-/2,2-dihalogenethenyl/-2,2-dimethylcyclopropancarboxyl acid as biologically active substance and method of its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS271126B1 (en) |
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1988
- 1988-06-16 CS CS884202A patent/CS271126B1/en unknown
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| Publication number | Publication date |
|---|---|
| CS420288A1 (en) | 1990-01-12 |
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