CS200161B2 - Method of producing d-trans-pyrethric acid - Google Patents
Method of producing d-trans-pyrethric acid Download PDFInfo
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- CS200161B2 CS200161B2 CS687671A CS767168A CS200161B2 CS 200161 B2 CS200161 B2 CS 200161B2 CS 687671 A CS687671 A CS 687671A CS 767168 A CS767168 A CS 767168A CS 200161 B2 CS200161 B2 CS 200161B2
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- trans
- acid
- alkali metal
- dimethyl
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- 238000000034 method Methods 0.000 title claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- -1 alkali metal salts Chemical class 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- PTQGFDXPHNRDCV-UHNVWZDZSA-N (1r,3r)-3-formyl-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)[C@H](C=O)[C@H]1C(O)=O PTQGFDXPHNRDCV-UHNVWZDZSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 3
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- DZWLWXNBYUMTSL-UHFFFAOYSA-N (1-methoxy-1-oxopropan-2-yl)phosphonic acid Chemical compound COC(=O)C(C)P(O)(O)=O DZWLWXNBYUMTSL-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 2
- 229960000948 quinine Drugs 0.000 abstract description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 abstract 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 abstract 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical class [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract 1
- 150000004714 phosphonium salts Chemical class 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 235000001258 Cinchona calisaya Nutrition 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- UIWNHGWOYRFCSF-UHFFFAOYSA-N Pyrethric acid Natural products COC(=O)C(C)=CC1C(C(O)=O)C1(C)C UIWNHGWOYRFCSF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- ACEONLNNWKIPTM-UHFFFAOYSA-N methyl 2-bromopropanoate Chemical compound COC(=O)C(C)Br ACEONLNNWKIPTM-UHFFFAOYSA-N 0.000 description 1
- SIGOIUCRXKUEIG-UHFFFAOYSA-N methyl 2-dimethoxyphosphorylacetate Chemical compound COC(=O)CP(=O)(OC)OC SIGOIUCRXKUEIG-UHFFFAOYSA-N 0.000 description 1
- STYUEUAAPQZSTL-UHFFFAOYSA-N methyl 2-dimethoxyphosphorylpropanoate Chemical compound COC(=O)C(C)P(=O)(OC)OC STYUEUAAPQZSTL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229940059835 pyrethrines Drugs 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C62/16—Saturated compounds containing —CHO groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
O výrobu této kyseliny je v současné době značný zájem vzhledem k tomu, že tato kyselina je složkou velmi účinných insekticidních přírodních pyrethrinů a syntetických esterů kyseliny d-trans-pyrethrové. Jakožto příklad uvedených esterů je možné uvést (5-benzyl) -3-furylmethylester kyseliny d-transpyrethrové, který vykazuje pozoruhodnou insekticidní účinnost.There is currently considerable interest in the production of this acid, since it is a component of highly effective insecticidal natural pyrethrines and synthetic d-trans-pyrethric acid esters. Examples of said esters include d-transpyrethric acid (5-benzyl) -3-furylmethyl ester, which has remarkable insecticidal activity.
Jediným dosud známým způsobem přípravy kyseliny d-trans-pyrethrové je hemisyntéza, popsaná v práci Matsui-ho et coli., publikované v Agr. Biol. Chem. Jap. 27, 373 (1963). Tato hemisyntéza představuje velmi náročný postup, při kterém se z výchozí kyseliny d-trans-chrysanthemové získá požadovaná kyselina d-trans-pyrethrová teprve po pěti reakčních stupních.The only method known to date for the preparation of d-trans-pyrethric acid is the hemisynthesis described in Matsui et al., Published in Agr. Biol. Chem. Me p. 27, 373 (1963). This hemisynthesis is a very difficult process in which the desired d-trans-pyrethyric acid is only obtained from the starting d-trans-chrysanthemic acid after only five reaction steps.
Výše uvedené nedostatky nemá způsob podle vynálezu, který umožňuje získat kyselinu d-trans-pyrethrovou v jediném reakčním stupni.The above drawbacks have no process according to the invention which makes it possible to obtain d-trans-pyrethric acid in a single reaction step.
Předmětem vynálezu je způsob výroby kyseliny d-trans-pyrethrové vzorce IThe present invention provides a process for the preparation of d-trans-pyrethric acid of the formula I
IIII
20D161 jehož podstata spočívá v tom, že se kyselina20D161, the nature of which is that of an acid
3,3-dimethyl-2- (R) -f ormyl-1- (R) -cyklopropankarboxylová vzorce II3,3-Dimethyl-2- (R) -formyl-1- (R) -cyclopropanecarboxylic acid of formula II
ΗΗ
uvede v reakci v přítomnosti bazického činidla, zvoleného ze skupiny zahrnující amid alkalického kovu, hydrid alkalického kovu, alkoholát alkalického kovu a alkalický kov, v organickém rozpouštědle, zvoleném ze skupiny zahrnující tetrahydrofuran, diethylether, dioxan, dimethoxyethan, alifatický alkohol, dimethylsulfoxid a dimethylformamid, s 0,0-dialkyl-l-methoxykarbonylethylfosfonátem obecného vzorce IIIreacting in the presence of a base selected from the group consisting of alkali metal amide, alkali metal hydride, alkali metal alcoholate and alkali metal in an organic solvent selected from tetrahydrofuran, diethyl ether, dioxane, dimethoxyethane, aliphatic alcohol, dimethylsulfoxide and dimethylformamide; with O, O-dialkyl-1-methoxycarbonylethylphosphonate III
CO-OCH.CO-OCH.
- H- H
(III) ve kterém R znamená alkylovou skupinu s(III) wherein R represents an alkyl group with s
I až 3 uhlíkovými atomy, načež se získaná kyselina d-trans-pyrethrová vyčistí.After 1 to 3 carbon atoms, the obtained d-trans-pyrethric acid is purified.
Kondenzace kyseliny 3,3-dimethyl-2- (R) -formy 1-1- (R) -cyklopropankarboxylové vzorce II s 0,0-dialkyl-l-methoxykarbonylethylfosfonátem obecného vzorce III se s výhodou provádí pod inertní atmosférou.The condensation of the 3,3-dimethyl-2- (R) -form 1-1- (R) -cyclopropanecarboxylic acid of formula II with the O, O-dialkyl-1-methoxycarbonylethylphosphonate of formula III is preferably carried out under an inert atmosphere.
Kyselina d-trans-pyrethrová získaná v surovém stavu se s výhodou vyčistí vytvořením soli, zvolené ze skupiny zahrnující sůl alkalického kovu, sůl L(+ )- nebo D( —)-threo-l-p-nitiOfenyl-2-N,N-dimethylaminopropanu a sůl 1-chininu.The raw d-trans-pyrethric acid is preferably purified by forming a salt selected from the group consisting of an alkali metal salt, an L (+) - or D (-) - threo-1β-nitrophenyl-2-N, N-dimethylaminopropane salt and 1-quinine salt.
Výchozí kyselinu 3,3-dimethyl-2-(R)-formyl-l-(R l-cyklopropankarboxylovou vzorce3,3-Dimethyl-2- (R) -formyl-1- (R1-cyclopropanecarboxylic acid) starting material
II (teplota varu při tlaku 120 Pa 115 °C; raln 25 = +36° + 1 při 1% koncentraci měřené látky v benzenu) lze získat oxidací kyseliny d-trans-chrysanthemové, popsanou pro racomát Rio Yamamoto-em v Scient. Papers Inst. Phys. Chem. Res. 3 193—222 (1925).II (boiling point at 120 Pa 115 ° C; ral n 25 = + 36 ° + 1 at 1% concentration of the test substance in benzene) can be obtained by oxidation of d-trans-chrysanthemic acid described for Rio Yamamoto racomate in Scient . Papers Inst. Phys. Chem. Res. 3,193-222 (1925).
Jakožto O,O-dialkyl-l-methoxykarbonylethylfosfonátu se s výhodou použije O,O-dimethyl- nebo O,O-diethyl-l-methoxykarbonylfosfonátu.O, O-dialkyl-1-methoxycarbonylethylphosphonate is preferably O, O-dimethyl or O, O-diethyl-1-methoxycarbonylphosphonate.
Ο,Ο-Dimethyl-l-methoxykarbonylethylfosfonát není dosud popsán v literatuře. Na základě analogie s přípravou alkylfosfoacetátů (Cf. Arbusov, Z. obšč, chim., 46, 297 a 61, 620] se O,O-dimethyl-l-methoxy-l-methyloxykarbonylethylfosfonát získá kondenzací trimethylfosfitu vzorce (СНзО)зР s methyl-tt-halogenpropionátem, kondenzací trimethylfosfonacetátu vzorce oΟ, Ο-Dimethyl-1-methoxycarbonylethylphosphonate is not yet described in the literature. By analogy with the preparation of alkylphosphoacetates (Cf. Arbusov, Z. obšč, chim., 46, 297 and 61, 620), O, O-dimethyl-1-methoxy-1-methyloxycarbonylethylphosphonate is obtained by condensation of trimethylphosphite of formula (СНзО) зР with methyl -t-halopropionate, by condensation of trimethylphosphonacetate of formula o
TT
P-CHj-COjCH^ na methyljodid v přítomnosti alkalického kovu nebo působením soli alkalického kovu dimethylfosfitu na methyl-a-halogenpropionát. Jeden příklad přípravy O,O,dimethyl-l-methoxykarbonylethylfosfonátu je uveden v příkladové části.’Methyl-iodide in the presence of an alkali metal or methyl-α-halopropionate by treatment of the alkali metal salt of dimethyl phosphite. One example of the preparation of O, O, dimethyl-1-methoxycarbonylethylphosphonate is given in the Examples section.
0,0-diethyl-l-methoxykarbonylethylfosfonát se připraví použitím metody H. W. Coocer-a et coli., popsané v J. Am. Chem. Soc. 79, str. 1963 (1957).O, O-diethyl-1-methoxycarbonylethylphosphonate was prepared using the method of H. W. Coocer et al., Described in J. Am. Chem. Soc. 79, 1963 (1957).
L(~P)- a D( — )-threo-l-p-nitrofenyl-2-N,Ndimethylaminopropan-l,3-diol jsou popsány ve francouzském patentu č. 1 481 978.L (-P) - and D (-) -threo-1-p-nitrophenyl-2-N, N-dimethylaminopropane-1,3-diol are described in French Patent No. 1,481,978.
Namísto fosfonátů obecného vzorce III je možné použít i jiných reakčních činidel, ze kterých lze uvést trialkylfosfoniové soli, zejména trifenyl-alkylfosfoniové soli, ze kterých účinkem silné báze vzniká alkylidenfosforan, a (tris-dialkylamino)alkylfosfoniové soli, [ (bis-dialkylamino)aryl]alkylfosfoniové soli a (dialkylaminodiaryl)alkylfosfoniové soli, ze kterých účinkem silné báze vzniká rovněž alkylidenfosforan, jakož i některé aktivní deriváty kyslíkatých sloučenin fosforu, které v přítomnosti silného bazického činidla reagují ve formě karbaniontu typuInstead of the phosphonates of formula III, other reagents may be used which include trialkylphosphonium salts, especially triphenyl-alkylphosphonium salts from which the strong base forms alkylidene phosphorane, and (tris-dialkylamino) alkylphosphonium salts, [(bis-dialkylamino) aryl] ] alkylphosphonium salts and (dialkylaminodiaryl) alkylphosphonium salts from which the strong base also produces alkylidene phosphorane, as well as certain active derivatives of oxygen-containing phosphorus compounds, which react in the presence of a strong basic agent in the form of a carbanion type
V následující části popisu je způsob podle vynálezu blíže objasněn formou příkladů provedení.In the following, the process according to the invention is explained in more detail by way of examples.
PříkladExample
Stupeň a:Stage a:
O,O-Dimethyl-l-methoxykarbonylethylfosfonáLO, O-Dimethyl-1-methoxycarbonylethylphosphonic acid
Pod atmosférou dusíku se smísí při teplotě 115 °C 124,1 g trimethylfosfidu a 183,7 g methyl-a-brompropionátu. Na uvedené teplotě se reakční směs udržuje po dobu 48 hodin. Po opětovném ochlazení se reakční směs rektifikuje za sníženého tlaku, přičemž se získá 76,9 g O,O-dimethyl-l-methoxykarbonylethylfosfonátu, který má teplotu varu 140 stupňů Celsia při tlaku 2,4 kPa.124.1 g of trimethylphosphide and 183.7 g of methyl .alpha.-bromopropionate are mixed at 115 DEG C. under a nitrogen atmosphere. The reaction mixture is maintained at this temperature for 48 hours. After cooling again, the reaction mixture is rectified under reduced pressure to give 76.9 g of O, O-dimethyl-1-methoxycarbonylethylphosphonate having a boiling point of 140 degrees Celsius at a pressure of 2.4 kPa.
Tento produkt může být bezprostředně použit pro kondenzaci s kyselinou 3,3-dimethyl-2- (R) -f ormyl-1- (R) formy l-cyklopropankarboxylovou.This product can be used immediately for condensation with 3,3-dimethyl-2- (R) -methyl-1- (R) form of 1-cyclopropanecarboxylic acid.
Číslo zmýdelnění získaného 0,0-dimethyl-1-methoxykarbonylethylfosfonátu je rovnoThe saponification number of the obtained 0,0-dimethyl-1-methoxycarbonylethylphosphonate is equal to
285 mg hydroxidu draselného na 1 g produktu.285 mg of potassium hydroxide per g of product.
Získaný O,O-dimethylll-methoxykarbonylethylfosfonát jt novou sloučeninou, která dosud nebyla popsána v literatuře.The O, O-dimethyl-11-methoxycarbonylethylphosphonate obtained is a novel compound not previously described in the literature.
Stupeň b:Stage b:
Kyselina d-trans-pyrethrová (kyselinaD - trans - pyrethric acid (acid
3.3- dimethyll2-(R)-(2‘-methoxykarbonyl-trans-r-propenyl) -1- (R) -cyklopropankarboxylová)3.3-Dimethyl-2- (R) - (2‘-methoxycarbonyl-trans-1-propenyl) -1- (R) -cyclopropanecarboxylic acid)
Do 40 ml tetrahydrofuranu se vnese 3,84 gramu amidu sodného 92% čistoty. Směs se potom ochladí na teplotu —5 °C, načež se do ní po kapkách vnese roztok 17,7 g O,O,-dimethyl-l-methoxykarbonylethylfosfonátu ve 40 ml tetrahydrofuranu. Reakční směs se zahřeje na teplotu 20 °C, při které se míchá po dobu tří hodin, načež se do ní vneseTo 40 ml of tetrahydrofuran was added 3.84 g of 92% pure sodium amide. The mixture was then cooled to -5 [deg.] C. and a solution of 17.7 g of O, O, -dimethyl-1-methoxycarbonylethylphosphonate in 40 ml of tetrahydrofuran was added dropwise. The reaction mixture was warmed to 20 ° C where it was stirred for three hours and then added.
1,92 g 92% amidu sodného. Reakční směs se znovu ochladí na teplotu —5 °C a po kapkách se do ní přidává roztok 6,4 g kyseliny1.92 g of 92% sodium amide. The reaction mixture was recooled to -5 ° C and a solution of 6.4 g of acid was added dropwise
3.3- dimethyl-2- (R) -f ormyl-l-cyklopropankarboxylové ve 40 ml tetrahydrofuranu. Reakční směs se potom zahřeje na teplotu 20 stupňů Celsia, na které se udržuje po dobu tří hodin a třiceti minut, načež se zahustí za sníženého tlaku.3.3-dimethyl-2- (R) -formyl-1-cyclopropanecarboxylic acid in 40 mL of tetrahydrofuran. The reaction mixture is then heated to 20 degrees Celsius for three hours and thirty minutes and then concentrated under reduced pressure.
Ke zbytku se přidá voda, vodná fáze se promyje etherem a spojené etherické extrakty se zase promyjí vodou. Vodná fáze se potom smísí a takto sloučená vodná fáze se okyselí na hodnotu pH 1 přídavkem vodného roztoku koncentrované kyseliny solné. Kyselá vodná fáze se extrahuje methylenchloridem a spojené methylenchloridové extrakty se promyjí vodou, vysuší a zahustí za sníženého tlaku.Water is added to the residue, the aqueous phase is washed with ether and the combined ether extracts are washed again with water. The aqueous phase is then mixed and the combined aqueous phase is acidified to pH 1 by addition of aqueous concentrated hydrochloric acid. The acidic aqueous phase is extracted with methylene chloride and the combined methylene chloride extracts are washed with water, dried and concentrated under reduced pressure.
Stupeň ci:Stage ci:
Přečištění získané kyseliny d-trans-pyretlirové vytvořením 1-chininové soliPurification of the obtained d-trans-pyretliric acid by formation of a 1-quinine salt
Zbytek z předcházejícího stupně o hmotnosti 9,48 g se rozpustí ve 100 ml acetonu, obsahujícího 16 % hmot. vody. K takto získanému roztoku se přidá roztok 12 g levotočivé chininové báze a reakční směs se zahřej na vodní lázni až k úplnému rozpuštění pevného podílu, načež se směs pomalu ochladí. Vyloučené krystaly se oddělí odstředěním, přičemž se získá 9,19 g surové 1-chninové soli.The residue from the preceding step (9.48 g) was dissolved in 100 ml of acetone containing 16% by weight of the title compound. water. A solution of 12 g of levorotatory quinine base is added to the solution thus obtained, and the reaction mixture is heated in a water bath until the solid is completely dissolved, and the mixture is cooled slowly. The separated crystals were collected by centrifugation to obtain 9.19 g of crude 1-quinine salt.
Z matečného louhu se získá další podíl stejné jakosti v množství 2,14 g.An additional portion of the same quality of 2.14 g was obtained from the mother liquor.
Oba získané podíly se spojí a překrystalizují z acetonu obsahujícího 16 % hmotnostních vody, přičemž se získá 7,5 g 1-chininové soli monomethylesteru kyseliny 1- (R ) -2- (R) -sek-tr ans-chr ysanthemdikarboxylové, která má teplotu tání 169 °C.The two fractions were combined and recrystallized from acetone containing 16% by weight of water to give 7.5 g of 1- (R) -2- (R) -sec-trans-isanthemedicarboxylic acid 1-quinine salt of monomethyl ester having mp 169 ° C.
[a']i)20 — —101 (1% koncentrace v methylalkoholu)[a] i) 20 - -101 (1% concentration in methanol)
Po přečištění matečního loúhu se získá druhý podíl stejné jakosti.After purification of the mother liquor, a second crop of the same quality is obtained.
Do 60 ml ethyletheru a 60 ml vodného roztoku 2 N kyseliny solné se vnese 7,5 g chininové soli, získané výše uvedeným postupem, směs se míchá, načež se etherické podíly oddělí dekantací. Oddělená etherická fáze se promyje vodou, tato promývací voda se extrahuje etherem a získané etherické podíly se opět spojí, vysuší a zahustí za sníženého tlaku.To 60 ml of ethyl ether and 60 ml of aqueous 2 N hydrochloric acid solution is added 7.5 g of the quinine salt obtained as above, the mixture is stirred and the ether is separated by decantation. The separated ethereal phase is washed with water, the washing water is extracted with ether and the ethereal fractions are combined, dried and concentrated under reduced pressure.
Zbytek se rektifikuje za sníženého tlaku, přičemž se získá 2,61 g kyseliny d-trans-pyrethrové (kyseliny 3,3-άΐηιοϋ^ 1-2-(И)-(2‘methoxykar bony Hrans-l ‘-propeny 1)-1-^)cyklopropankarboxylové, která má teplotu varu 130 °C při tlaku 26,6 Pa.The residue is rectified under reduced pressure to give 2.61 g of d-trans-pyrethyric acid (3,3-trans-1,2,3- (2-methoxycarbone Hrans-1'-propenyl)) - 1- (4) cyclopropanecarboxylic acid having a boiling point of 130 ° C at a pressure of 26.6 Pa.
Í«)d20 = -+81° (1,2% koncentrace ve chloridu uhličitém)««) D 2 0 = - + 81 ° (1,2% concentration in carbon tetrachloride)
Analýza:Analysis:
CiiHieOá (212,24)CiiHieOá (212.24)
Vypočteno:Calculated:
62,25 % C, 7,60 % H,% C, 62.25;% H, 7.60.
Nalezeno:Found:
62,5 % C, 7,8 % H.% C, 62.5;% H, 7.8%.
Ultrafialové spektrum:Ultraviolet spectrum:
(ethylalkohol)(ethyl alcohol)
Maximum při 238—239 nm (ε = 15 100)Maximum at 238—239 nm (ε = 15 100)
Infračervené spektrum:Infrared spectrum:
(chloroform)(chloroform)
Získané infračervené spektrum je shodné se spektrem, popsaným autory Matsui et al. v Agr. Biol. Chem. Jap. 27 (1963) 374.The infrared spectrum obtained is identical to that described by Matsui et al. in Agr. Biol. Chem. Me p. 27 (1963) 374.
NMR-dpektrum:NMR-Spectrum:
(deuterochlorof orm) (ref. == 60 MHz)(deuterochlorophore) (ref. = 60 MHz)
Bylo získáno NMR-spektrum, které je v souladu s konfigurací trans kruhu a s konfigurací trans olefinového řetězce:An NMR spectrum was obtained which was consistent with the trans ring configuration and the trans olefin chain configuration:
a 83 MHz (odpovídá vodíkům methylových skupin v poloze 3),and 83 MHz (corresponds to the hydrogens of the methyl groups at the 3-position),
101.5— 107 MHz [odpovídá vodíku v poloze 1 (dublet)),101.5—107 MHz (corresponds to hydrogen at position 1 (doublet)),
117.5— 119 MHz (odpovídá vodíkům methylové skupiny postranního řetězce), β117.5 - 119 MHz (corresponding to the side chain methyl group hydrogen), β
128—138—143 MHz [odpovídá vodíku v poloze 2 (triplet·)],128—138—143 MHz [corresponds to hydrogen in position 2 (triplet ·)],
227,5 MHz (odpovídá vodíkům methylové skupiny v esterové skupině),227.5 MHz (corresponds to the hydrogens of the methyl group in the ester group),
387—397 MHz [odpovídá vodíkům na uhlících spojených dvojnou vazbou v postranním řetězci (dublet)],387–397 MHz [corresponds to hydrogens on carbons linked by a double bond in the side chain (doublet)],
664 MHz (odpovídá vodíku skupiny664 MHz (corresponds to hydrogen of the
C—OH v poloze 1).C-OH in position 1).
Cirk, dichroismus:Cirk, dichroism:
(dioxan)(dioxane)
Maximum při 232 nm; Δε = 7,98.Maximum at 232 nm; Δε = 7.98.
Nahrádí-li se O,O-dimethyl-l-methoxykarbonylethylfosfonát odpovídajícím O,O-diethyl-derivátem, získají se obdobné výsledky.When O, O-dimethyl-1-methoxycarbonylethylphosphonate is replaced by the corresponding O, O-diethyl derivative, similar results are obtained.
Stupeň C2Step C2
Přečištění získané kyseliny d-trans-pyrethrové vytvoření sodné soliPurification of the obtained d-trans-pyrethric acid to form the sodium salt
Zbytek ze stupně b o hmotnosti 9,49 g se rozpustí v 60 ml acetonu a k ní získanému roztoku se přidá 4,5 ml vodného roztoku 10 N hydroxidu sodného. Vykrystalizuje sod ná sůl. Vyloučené krystaly se odpaří při teplotě 0 až 5 °C a promyjí acetonem. Získaná sodná sůl kyseliny d-trans-pyrethové má [a]o20 = 56 ° + 2 . (1% koncentrace vzorku ve vodě).The residue from step b (9.49 g) was dissolved in 60 ml of acetone and 4.5 ml of aqueous 10 N sodium hydroxide solution was added thereto. The sodium salt crystallizes. The precipitated crystals are evaporated at 0-5 ° C and washed with acetone. The obtained d-trans-pyrethic acid sodium salt has [α] D 20 = 56 ° +2. (1% sample concentration in water).
Získaný produkt je rozpustný ve vodě a nerozpustný v acetonu a v etheru.The product obtained is soluble in water and insoluble in acetone and ether.
Dále se postupuje stejně jako ve stupni ci k získání kyseliny d-trans-pyrethrové.The procedure is followed as in step c to obtain d-trans-pyrethric acid.
Stupeň C3Grade C3
Přečištění získané kyseliny d-trans-pyrethrové vytvořením soli s (L-(—--thero-1-p-nitrofenyl-2-N,N-dimethylaminopropan-1,3-diolemPurification of the obtained d-trans-pyrethric acid by salt formation with (L - (- - thero-1-p-nitrophenyl-2-N, N-dimethylaminopropane-1,3-diol)
Zbytek stupně b o hmotnosti 9,48 g se rozpustí ve 30 ml ethylacetátu, načež se k získanému roztoku přidá 11,1 g (L-(-(-)-threo-l-p-nitrofenyl-2-N,N-dimethylaminopropan-1,3-diolu a směs se zahřívá pod zpětným chladičem až k úplnému rozpuštění pevného podílu. Směs se potom ochladí na teplotu 0 až 5 °C, přičemž vykrystalizuje výše uvedená sůl, která se odstředí a promyje ethylacetátem.The residue (b) of 9.48 g is dissolved in 30 ml of ethyl acetate, and 11.1 g of (L - (- (-) - threo-1β-nitrophenyl-2-N, N-dimethylaminopropane-1, 3-diol and the mixture was heated to reflux until the solid was completely dissolved, then the mixture was cooled to 0-5 [deg.] C, whereupon the above salt crystallized, which was centrifuged and washed with ethyl acetate.
Získá se 11,4 g kyseliny d-trans-pyrethrové ve formě soli s L-(-|-3-threOll-plmtrofenyl-2-N,N-dimethylaminopгopan-l,3-diolem.11.4 g of d-trans-pyrethyric acid are obtained in the form of a salt with L - (-? - 3-threo-11-pltrophenyl-2-N, N-dimethylaminopropane-1,3-diol).
Získaný produkt má bledě žlutou barvu a taje při teplotě 125 °C.The product obtained is pale yellow in color and melts at 125 ° C.
[folD20 1 — + 52° ' + 2 (1% koncentrace vzorku v ethylalkoholu).[folD 2 0 1 - + 52 ° + 2 (1% concentration of sample in ethanol).
Produkt je rozpustný v . methylalkoholu a acetonu a omezeně rozpustný ve vodě, etheru a ethylacetátu. 'Tento produkt dosud nebyl popsán v literatuře.The product is soluble in. methanol and acetone and sparingly soluble in water, ether and ethyl acetate. This product has not yet been described in the literature.
Dále se postupuje stejně jako uvedeno ve stupni ci k získání kyseliny d-trans-pyrethrDl vé.The procedure is followed as described in step c to obtain d-trans-pyrethyric acid.
předmět vynalezuthe subject of the invention
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR127745 | 1967-11-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS200161B2 true CS200161B2 (en) | 1980-08-29 |
Family
ID=8641542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS687671A CS200161B2 (en) | 1967-11-10 | 1968-11-11 | Method of producing d-trans-pyrethric acid |
Country Status (13)
| Country | Link |
|---|---|
| AT (1) | AT286960B (en) |
| CH (1) | CH498797A (en) |
| CS (1) | CS200161B2 (en) |
| DE (2) | DE1807091B2 (en) |
| DK (1) | DK144941C (en) |
| FR (1) | FR1579476A (en) |
| GB (2) | GB1246813A (en) |
| IL (1) | IL30905A (en) |
| NL (2) | NL6815987A (en) |
| PL (1) | PL69854B1 (en) |
| SE (1) | SE353709B (en) |
| SU (1) | SU423290A3 (en) |
| YU (1) | YU34271B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2730515A1 (en) * | 1977-07-06 | 1979-01-18 | Bayer Ag | SUBSTITUTED PHENOXYBENZYLOXYCARBONYL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES |
| US4296241A (en) * | 1979-07-21 | 1981-10-20 | Bayer Aktiengesellschaft | Preparation of 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropane-1-carboxylic acid derivatives |
-
0
- NL NL133054D patent/NL133054C/xx active
-
1967
- 1967-11-10 FR FR127745A patent/FR1579476A/fr not_active Expired
-
1968
- 1968-10-21 IL IL30905A patent/IL30905A/en unknown
- 1968-11-01 CH CH1633668A patent/CH498797A/en not_active IP Right Cessation
- 1968-11-01 DK DK530268A patent/DK144941C/en not_active IP Right Cessation
- 1968-11-05 DE DE19681807091 patent/DE1807091B2/en active Granted
- 1968-11-05 DE DE19681817881 patent/DE1817881A1/en active Granted
- 1968-11-06 SU SU1283233A patent/SU423290A3/ru active
- 1968-11-06 YU YU2608/68A patent/YU34271B/en unknown
- 1968-11-08 NL NL6815987A patent/NL6815987A/xx unknown
- 1968-11-08 SE SE15201/68A patent/SE353709B/xx unknown
- 1968-11-08 PL PL1968129971A patent/PL69854B1/pl unknown
- 1968-11-11 CS CS687671A patent/CS200161B2/en unknown
- 1968-11-11 GB GB53375/68A patent/GB1246813A/en not_active Expired
- 1968-11-11 GB GB4197/71A patent/GB1246814A/en not_active Expired
- 1968-11-11 AT AT1096168A patent/AT286960B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| SE353709B (en) | 1973-02-12 |
| DE1807091C3 (en) | 1973-11-08 |
| DE1817881A1 (en) | 1973-03-08 |
| IL30905A0 (en) | 1968-12-26 |
| YU260868A (en) | 1978-10-31 |
| SU423290A3 (en) | 1974-04-05 |
| DE1807091B2 (en) | 1973-04-19 |
| CH498797A (en) | 1970-11-15 |
| DK144941C (en) | 1982-11-29 |
| IL30905A (en) | 1972-08-30 |
| PL69854B1 (en) | 1973-10-31 |
| NL133054C (en) | |
| NL6815987A (en) | 1969-05-13 |
| AT286960B (en) | 1971-01-11 |
| DE1817881C3 (en) | 1979-08-02 |
| FR1579476A (en) | 1969-08-29 |
| YU34271B (en) | 1979-04-30 |
| GB1246813A (en) | 1971-09-22 |
| GB1246814A (en) | 1971-09-22 |
| DE1817881B2 (en) | 1978-11-23 |
| DE1807091A1 (en) | 1969-10-02 |
| DK144941B (en) | 1982-07-12 |
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