IE53149B1 - Novel 4-(3'-trifluoromethylphenoxy)-benzoylacetic acid derivatives - Google Patents
Novel 4-(3'-trifluoromethylphenoxy)-benzoylacetic acid derivativesInfo
- Publication number
- IE53149B1 IE53149B1 IE1642/87A IE164287A IE53149B1 IE 53149 B1 IE53149 B1 IE 53149B1 IE 1642/87 A IE1642/87 A IE 1642/87A IE 164287 A IE164287 A IE 164287A IE 53149 B1 IE53149 B1 IE 53149B1
- Authority
- IE
- Ireland
- Prior art keywords
- formula
- trifluoromethylphenoxy
- novel
- acid derivatives
- acid derivative
- Prior art date
Links
- SKYYIVRRDMVLGY-UHFFFAOYSA-N 3-oxo-3-[4-[3-(trifluoromethyl)phenoxy]phenyl]propanoic acid Chemical class C1=CC(C(=O)CC(=O)O)=CC=C1OC1=CC=CC(C(F)(F)F)=C1 SKYYIVRRDMVLGY-UHFFFAOYSA-N 0.000 title claims description 5
- -1 propargyloxy Chemical group 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000005336 allyloxy group Chemical group 0.000 claims description 2
- 150000004653 carbonic acids Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- OTJFQRMIRKXXRS-UHFFFAOYSA-N (hydroxymethylamino)methanol Chemical compound OCNCO OTJFQRMIRKXXRS-UHFFFAOYSA-N 0.000 description 1
- 125000004793 2,2,2-trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 description 1
- PQOCJONTQYLEFC-UHFFFAOYSA-N 3-methoxy-3-oxopropanoic acid;hydrochloride Chemical compound Cl.COC(=O)CC(O)=O PQOCJONTQYLEFC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 229910004373 HOAc Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 150000003940 butylamines Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 229940087646 methanolamine Drugs 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
The invention relates to novel 4-(3’-trifluoromethylphenoxy)-benzoylacetic acid derivatives of formula II
R J χ • z «
I II • · / \ (II), \/VFi • · η ι wherein R3 is Ci-Ci,-alkoxy, allyloxy, propargyloxy, 2,2,2-tri5 ch'loroethoxy, 2,2,2-trifluoroethoxy, 2-chloroethoxy, C2-Cs-alkoxyalkoxy, hydroxy or salts of those carbonic acids.
The compounds of formula XI are valuable intermediates for the synthesis of novel herbicidally active pyrones of formula I Rl\ z’\ zc Rs r/W \ 2 I II (I), \ I II \/ ;-CF3 wherein Rj and R2 independently of one another are each a Cj-Ci,alkyl group, or one of the two substituents is also hydrogen or Ri and R2 jointly form a C2-C6-alkylene bridge and R3 is as defined in formula II.
53146
Cj-Cii-alkyl as substituent or as part of a substituent Is n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl and in particular methyl and ethyl.
Suitable salts are in particular metal salts, and salts with quaternary ammonium bases or organic nitrogen bases. Metals suitable for salt formation are for example: alkaline-earth metals, such as magnesium or calcium, especially however the alkali metals, such as lithium, potassium or sodium. Also applicable as salt formers are transition metals, such as iron, nickel, cobalt, copper, zine, chromium or manganese.
Examples of quaternary ammonium bases are the ammonium cation, tetraalkylammonium cations in which the alkyl groups independently of one another are straight-chain or branched-chain Ci-Ci-alkyl groups, such as the tetramethylaramonium cation, the tetraethylammonium cation or the trimethylethylammonium cation, and also the trimethylbenzylaromoniurn cation, the triethylbenzylammonium cation, the trimethyl-2-hydroxyethylammonium cation and the trimethyl-2chloroethylammonium cation.
Example of organic nitrogen bases suitable for forming salts are: primary, secondary and tertiary, aliphatic and aromatic amines which can be hydroxylated on the hydrocarbon radical, such as: methylamine, ethylamine, propylamine, isopropylamine, the four Isomeric butylamines, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, pyrrolidine, piperidine, morpholine, trimethylamine, triethylamine, tri-n-propylamine, quinuclidine, pyridine, quinoline, isoqulnoline as well as methanolamine, ethanolamine, propanolamine, dimethanolamine, diethanolamine or triethanolamine.
Compounds of the formula I are produced, using a process analogous to that described in Bull. Soc. Chim. de France (1968), 288-298, by
53148
a) reacting a compound of the formula IX
C-Rj
CH2
I II \A (II) \ A /CFj
II I wherein Ra has the meaning mentioned above, in an inert solvent, with a compound of the formula III
Mg(OR’)t (III) wherein R' is a straight chain or branched-chain Ci-Ci,-alkyl group;
b) reacting the resulting reaction product, in an inert solvent, with a compound of the formula V
Rz—CH=C—e—Cl (V) wherein Ri and Ra have the same meaning as given above and
c) cyclising the resulting product with an alcoholic solution of a strong acid, and, when R3 in the formula I is hydroxyl, saponifying the ester obtained, or optionally converting in the resulting ester of the formula I the group R3 , by transesterification, into another group R3 defined under the formula I.
The reactions described under a) and b) are in each case performed in an inert solvent. Suitable inert solvents are for example: benzene, toluene, xylene, ether, tetrahydrofuran or dioxane.
53148
The reaction of a compound of the formula XI with a compound of the formula III is advantageously performed at a temperature within the range of 0 to 150°C; and the reaction of the reaction product obtained under a) with a compound of the formula V at a temperature within the range of -10°C to room temperature.
The magnesium alcoholate of the formula III used in the reaction described under a) can be produced in situ by reaction of magnesium with a corresponding alcohol in the presence of CCli,.
The cyclisation described under c) can be performed with an alcoholic solution of a catalytic amount of a strong acid under reflux, for example with an alcoholic solution of hydrochloric acid, which is also obtainable in situ by reaction of acetyl chloride with alcohol.
The conversion of a group Ra into another group R3 defined under the formula I by transesterification can be carried out, in a manner known per se, by adding to a compound of the formula I a corresponding alchohol in the presence of a strong acid.
The new compounds of formula II have especially been developed for the synthesis of compounds of formula I.
In the German Offenlegungsschrift No. 2,436,012 are described 4-phenoxy-bentoylacetic acid and alkyl esters thereof in which the phenoxy group is unsubstituted or substituted by a fluorine, chlorine or bromine atom or by a trifluorometbyl group. The alkyl esters are obtainable by Friedel-Crafts acylation of the corresponding diphenyl ethers with malonic ester chlorides, and the corresponding acids by subsequent saponification.
(5
In addition to being obtainable by the processes already mentioned in the foregoing, compounds of the formula II can also be produced, using a process analogous to that described in J. Amer. Chem*
Soc. 70 (1948), 3356-3360, by reaction of phenoxyphenyl derivatives with malonic acid methyl ester chloride.
Furthermore, compounds of the formula II in which R3 is Ci-Ci,-alkoxy can be produced, using a process analogous to that described in Tetrahedron 20 (1964), 1625-1632, according to the following reaction scheme:
CH3 .
ΐ ii \x\/CF3 fi ί
C-Rj
1) NaH (2 equiv) yHj dioxane
R7O—C—OR7 2) HOAc \ 7 \
I II • ·
II I (VIII) (II)
In the above formulae R7 is Ci-Ci,-alkyl.
The compound of the formula VIII is known and can be produced by methods analogous to known methods (cf. for example US Patent Specification No. 4,125,729; and Belgian Patent Specification No. 639,727 [Ref. in Chem. Abst. 62 (1965), 14581h]).
Production Example for compounds of formula XX
Example; 4-(3'-Trifluoromethyl-phenoxy)-benzoylaeetic acid methyl ester (Compound 1 in table 1).
To a mixture of 29 g of NaH (2 equiv.; 55 % oil dispersion, washed three times with toluene) and 54 g of dimethylcarbonate in 400 ml of dioxane are added dropwise, at 85°C, 84,2 g of 4-(3'-trifluoromethylphenoxy)-acetophenone dissolved in 160 ml of dioxane, whereupon an evolution of hydrogen immediately occurs. After the reaction has subsided, the reaction mixture is stirredd at 85°C for a further
2 hours, and 100 ml of acetic acid are then added dropwise with ice cooling. To the paste obtained are added 400 ml of ether and about 200 g of neutral Alox 1 (aluminium oxide (alumina) Woelm, activity stage I), and the mixture is filtered. The filtrate is concentrated by evaporation, dissolved in acetone, washed successively with water, a saturated NaHCOa solution and a saturated NaCl solution, dried, and concentrated by evaporation. The viscous product obtained can be used directly for the production of compounds of the for_2 mula I, or it is distilled at 10 Torr and 160°C, or recrystallised from hexane (m.p. 50 - 55°C). The yield of pure product is about
65 g (65 % of theory).
The following compounds of the analogous manner:
formula II can be produced ln an
Rj
A a
I fi (II), « I
Table 1:
Nr. Ra Smp °C (constitution) 1 OCHa 50 - 55 2 OC2Hs (viscous) 3 OC3H7ISO (viscous) 4 OCsHgtert - 5 0CaH7n (viscous) 6 OCqHgn (viscous) 7 OCH2CH2C1 - 8 0CH2CH=CH2 - . 9 0CH2CSCH - 10 OCH2CH2OCH3 - 11 OCH2CF3 -
Claims (4)
1. A 4-(3‘-trifluoromethylphenoxy)benzoyl-aeetie acid derivative of formula XI II I (II), 5 wherein Ra is Cj-Cq-alkoxy, allyloxy, propargyloxy, 2,2,2-fcrichloroethoxy, 2,2,2-trifluoroethoxy, 2-chloroethoxy, Cj-Cs-alkoxyalkoxy, hydroxy or a salt of those carbonic acids.
2. A 4-(3'-trifluoromethylphenoxy)benzoyl-acetic acid derivative of the formula II given and defined in Claim 1 or a possible salt 10 thereof, substantially as hereinbefore described and exemplified.
3. A process for preparing a 4-(3'-trifluoromethylphenoxy)benzoylacetic acid derivative of the formula II given and defined in Claim 1 or a possible salt thereof, substantially as hereinbefore described and exemplified. 15
4. A 4-(3'-trifluoromethylphenoxy)benzoyl-acetic acid derivative of the formula II given and defined in Claim 1 or a possible salt thereof, whenever prepared by a process claimed in Claim 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH363081 | 1981-06-03 | ||
| IE1329/82A IE53148B1 (en) | 1981-06-03 | 1982-06-02 | Novel dihydropyrones,process for producing them,compositions containing the novel dihydropyrones as active ingredients,and the use thereof for combating weeds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE871642L IE871642L (en) | 1982-12-03 |
| IE53149B1 true IE53149B1 (en) | 1988-07-20 |
Family
ID=25693472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE1642/87A IE53149B1 (en) | 1981-06-03 | 1982-06-02 | Novel 4-(3'-trifluoromethylphenoxy)-benzoylacetic acid derivatives |
Country Status (1)
| Country | Link |
|---|---|
| IE (1) | IE53149B1 (en) |
-
1982
- 1982-06-02 IE IE1642/87A patent/IE53149B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IE871642L (en) | 1982-12-03 |
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