GB1560711A - Isoxazoles and manufacture thereof - Google Patents
Isoxazoles and manufacture thereof Download PDFInfo
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- GB1560711A GB1560711A GB45888/76A GB4588876A GB1560711A GB 1560711 A GB1560711 A GB 1560711A GB 45888/76 A GB45888/76 A GB 45888/76A GB 4588876 A GB4588876 A GB 4588876A GB 1560711 A GB1560711 A GB 1560711A
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- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000002545 isoxazoles Chemical class 0.000 title description 10
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 150000002825 nitriles Chemical class 0.000 claims description 17
- -1 acetylene compound Chemical class 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000012433 hydrogen halide Substances 0.000 claims description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000005108 alkenylthio group Chemical group 0.000 claims description 2
- 125000003282 alkyl amino group Chemical group 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 230000000361 pesticidal effect Effects 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VGLOEMGOLOYOIX-UHFFFAOYSA-N 1-methoxy-2-nitroethane Chemical compound COCC[N+]([O-])=O VGLOEMGOLOYOIX-UHFFFAOYSA-N 0.000 description 1
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GOKVGHZDRFITKL-UHFFFAOYSA-N 3-(1-chloroethyl)-5-methyl-1,2-oxazole Chemical compound CC(Cl)C=1C=C(C)ON=1 GOKVGHZDRFITKL-UHFFFAOYSA-N 0.000 description 1
- YFWMGDSBMTZTQY-UHFFFAOYSA-N 5-(1-bromoethyl)-3-ethyl-1,2-oxazole Chemical compound BrC(C)C1=CC(=NO1)CC YFWMGDSBMTZTQY-UHFFFAOYSA-N 0.000 description 1
- SGGYGPPIFVYPHA-UHFFFAOYSA-N 5-(chloromethyl)-3-(methoxymethyl)-1,2-oxazole Chemical compound COCC=1C=C(CCl)ON=1 SGGYGPPIFVYPHA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-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 compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241001061127 Thione Species 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine 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
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- RNSUNNOEBOGKHG-UHFFFAOYSA-N n-hydroxyethanimidoyl chloride Chemical compound CC(Cl)=NO RNSUNNOEBOGKHG-UHFFFAOYSA-N 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- LJZPPWWHKPGCHS-UHFFFAOYSA-N propargyl chloride Chemical compound ClCC#C LJZPPWWHKPGCHS-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 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
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
- C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/653—Five-membered rings
Landscapes
- 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)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Description
(54) NEW ISOXAZOLES AND MANUFACTURE
THEREOF
(71) We, BASF AKTIENGESELLSCHAFT, a German Joint Stock Com pany of 6700 Ludwigshafen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention provides new compounds of the general formula
wherein R1 denotes linear or branched, unsubstituted or halogen-, alkoxy- or alkylthiosubstituted C1 to C10 alkl, R2 denotes linear or branched C, to C, alkyl or, provided that R1 contains 4 or more carbon atoms and/or a halogen oxygen or sulfur atom, hydrogen, and X denotes halogen. Isoxazoles of the general formula I are valuable intermediates for the production of biologically active compounds.
The present invention further provides a process for the manufacture of the new isoxazoles of the general formula I by reaction of nitrile oxides of the general formula
II with acetylene compounds of the general formula III, Rt, R2 and X having the meanings given above.
It is surprising that nitrile oxides of the general formula II do not react with acetylene compounds of the general formula III to give isoxazoles of the general formula IX, but that, in a regiospecific reaction, isoxazoles of the general formula I according to the invention are formed:
because it is known from Grundmann (Houben-Weyl, Methoden der organischen Chemie, 10/3, p. 860, Georg Thieme-Verlag, Stuttgart, 4th ed., 1965) that in reactions of nitrile oxides with acetylene compounds nitrile oxides of the general formula VI add on to acetylene compounds of the general formula VII in such a manner that the centres of the opposing partial charges face each other. The chemical bond between these centres then results in isoxazole derivatives of the general formula VIII:
Since the following partial charge distributions (C. K. Ingold, Structure and
Mechanism in Organic Chemistry, Cornell University Press, Ithaca, New York, 1953, p. 149) are present as a result of the negative induction effect of halogen atoms in the acetylene compounds of the general formula III:
the nitrile oxides of the general formula II would have been expected to add on to the acetylene compounds of the general formula III in accordance with Grundmann' 5 scheme to give isoxazoles of the general formula IX:
The nitrile oxides of the general formula II required as starting compounds may be easily prepared by generally known processes (Houben-Weyl, Methoden der organischen Chemie, 10/3, p. 837, George Thieme-Verlag, Stuttgart, 4th ed., 1965;
J. Org. Chem., 28, 1150, 1963), for instance by reaction of aliphatic nitro compounds of the general formula IV with water-eliminating agents or by dehydrohalogenation of hydroxamic halides, especially chlorides, of the general formula V.
Aliphatic nitro compounds may be prepared by the processes described in Houben
Weyl, Methoden der organischen Chemie, 10/1, pp. 1461, George Thierne-Verlag, Stuttgart, 4th ed., 1971, and hydroxamic halides by the processes described in Houben
Weyl, Methoden der organischen Chemie, 10/4, pp. 98-128, George Thieme-Verlag,
Stuttgart, 4th ed.
The nitrile oxides of the general formula II and the acetylene compounds of the general formula III may be reacted in equimolar amounts; alternatively, either of the two reactants may be used in excess.
It is, however, not necessary to isolate the nitrile oxides of the general formula II before the reaction of the invention; indeed it is advantageous to produce the nitrile oxides of the general formula II in the presence of the acetylene compounds of the general formula III. The reactive nitrile oxides then react in situ with the acetylene compounds to give isoxazoles of the general formula I according to the invention.
A suitable solvent in which the reaction proceeds is an excess of the acetylene compound of the general formula m. Examples of other suitable solvents are aromatic compounds, such as benzene, toluene, xylene and halogenated aromatic compounds; ketones, such as acetone, methyl ethyl ketone and diisopropyl ketone; ethers, such as dioxane, diethyl ether and tetrahydrofuran; and chlorinated hydrocarbons, such as dichloroethane, chloroform and methylene chloride.
It is advantageous to carry out the reaction at atmospheric pressure and temperatures of from 200 to + 1500 C; temperatures of from 0 to 100"C are preferred.
To bind hydrogen halide formed in the reaction it is expedient to add a base, e.g., a tertiary amine.
Individual examples of radicals R' are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the branched isomers of these alkyl radicals. The same applies to radicals R2 with 1 to 6 carbon atoms. Examples of ether and thioether groups R1 are methoxypropyl, ethoxypropyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl and the corresponding thioethers.
Fluorine, chlorine, bromine and iodine are suitable as halogen in radicals R1 and as X. An example of a halogen-substituted radical R1 is trifluoromethyl.
The structure of the starting compounds corresponds to the substituents in the compounds of the invention.
Individual compounds according to the invention are as follows:
R1 R2 X ClI3 CH3 Br i-C3H, CH, Cl
i-C3H7 C2H5 Cl CH,OCH,- H C1 i-C,H,--SS-CH, CH3 Br CiCH2- H Br
F,C H Br
The following examples illustrate the process for the manufacture of these compounds of the invention. The structure of the isoxazoles obtained may be established with the aid of 'H-NMR spectroscopy and 13C-NMR spectroscopy.
Parts by weight bear the same relation to parts by volume as kilograms to liters.
EXAMPLE 1
149 parts by weight of propargyl chloride, 476 parts by weight of phenyl iso
cyanate and 210 parts by weight of 2-methoxynitroethane are dissolved in 1,500 parts
by volume of toluene; at 15 to 20"C, 1 part by volume of triethylamine is then added to activate the phenyl isocyanate. The temperature is kept for 3 hours at 150 to 300C,
1 part by volume of uiethylamine being added per hour. Subsequently, the mixture is stirred for 1 hour at 70"C, and then cooled. The precipitate is suction filtered and the residue washed with 1,000 parts by volume of toluene. The combined filtrates are concentrated and the residue is distilled under an oil pump vacuum. 5-chloromethyl3-methoxymethyl-isoxazole distils over.
EXAMPLE 2
93.5 parts by weight of acetohydroximoyl chloride (Ber. dtsch. chem. Ges., 40, 1677, 1907) and 90 parts by weight of isobutynyl chloride are stirred into 1,500 ml of benzene; at 15" to 20"C, 105 parts by weight of triethylamine is then added drop wise. The mixture is then stirred for 1 hour at 20 to 25"C and for 1 hour at 70 C.
After cooling, the mixture is filtered and the filtrate concentrated. The distillate which remains is distilled under an oil pump vacuum. There is obtained 133 parts by weight (92% of theory) of 3-(1-chloroethyl)-5-methyl isoxazole having a boiling point of 48" to 50"C/0.05 mm Hg; nod25: 1.4740.
C,HaNOCL (145.5)
Calc.: C, 49.6; H, 5.5; N, 9.7; Cl, 24.5
Found: C, 49.5; H, 5.7; N, 10.0; Cl, 24.0
60 MHz nmr spectrum (CDCl; 3 values): 1.78 (d, 3H); 2.3 (s, 3H); 5.05 (9, lH); 6.09 (s, 1H).
3C mur spectrum (CDCl3; ppm values relative to TMS): 171.5 (C); 159.8 (C); 102.5 (CH); 47.4 (CH); 23.3 (CHs); 11.5 (CHs).
EXAMPLE 3
133 parts by weight of emethyl-propargyl bromide, 95 parts by weight of nitropropane and 440 parts by weight of triethylamine are dissolved in 1,200 parts by volume of chloroform; at 0 C, 155 parts by weight of phosphoroxy chloride is then added dropwise. The mixture is then heated for 30 minutes at 20"C and then reflexed for 2 hours. After cooling, the mixture is filtered and concentrated, and the residue is taken up in water. The water phase is extracted again with toluene, and the combined toluene phases are washed with water and then dried over sodium sulfate. The sodium sulfate is then separated and the filtrate concentrated; the residue is distilled under an oil pump vacuum.
5-(1-bromoethyl)-3ethyl isoxazole distils over:
The following compounds are obtained analogously:
The significance of the new compounds lies firstly in their basic isoxazole structure and secondly in the substituent
in which the halogen X can readily be exchanged for other radicals which themselves can have a biological action or, for instance by changing lyophilic properties, only have auxiliary functions. The new compounds are thus suitable for the manufacture of various insecticides, herbicides, fungicides and nematocides; of particular importance are derivatives of phosphoric and phosphonic acid and their corresponding thiol, thione and thionothiol derivatives.
The phosphoric acid derivatives are obtained by reacting salts of phosphoric acid derivatives of the general formula XIII with isoxazole derivatives of the general formula
I to give the phosphoric acid derivatives of the general formula XIV:
The radicals R1, R3 and X have the above meanings, Z denotes an alkali metal ion, an equivalent amount of an alkaline earth metal ion, or an ammonium ion optionally substituted by alkyl radicals, Y denotes oxygen or sulfur, R3 denotes linear or branched alkoxy of a maximum of 6 carbon atoms, linear or branched alkylthio, alkenylthio or alkylnylthio of a maximum of 6 carbon atoms, alkyl of a maximum of 3 carbon atoms, phenyl, or linear or branched alkylamino or dialkylamino of a maximum of 5 carbon atoms, and R4 denotes linear or branched alkyl of a maximum of 6 carbon atoms.
Phosphoric acid derivatives of the general formula XIV are described and claimed in our copending UK patent application No. 45889/76 (Serial No. 1,560,712). Further information on such compounds, their production and their pesticidal use is to be found in that application, to which attention is directed.
WHAT WE CLAIM IS:- 1. Compounds of the general formula
where R1 denotes linear or branched, unsubstituted or halogen-, alkoxy- or alkylthiosubstituted C1 to C,0 alkyl, R2 denotes linear or branched C1 to C, alkyl or, provided that R' contains 4 or more carbon atoms and/or a halogen, oxygen or sulfur atom, hydrogen, and X denotes halogen.
2. A process for producing a compound as claimed in claim 1, wherein a nitrile oxide of the general formula R1-C=-NO II ee where R1 has the meaning given in claim 1, is reacted with an acetylene compound of the general formula
where R2 and X have the meanings given in claim 1, in the presence or absence of a solvent.
3. A process as claimed in claim 2 carried out at from -20 to +150 C 4. A process as claimed in claim 2 or 3, wherein the nitrile oxide is formed in situ from the corresponding aliphatic nitro compound by elimination of water, or from the corresponding hydroxamic acid halide by dehydrohalogenation.
5. A process as claimed in any of claims 2 to 4, wherein the reaction of the nitrile oxide is carried out in the presence of a tertiary amine to bind hydrogen halide formed.
6. A process as claimed in any of claims 2 to 5, wherein the reaction of the nitrile oxide is carried out in the presence of excess acetylene compound III serving as solvent.
7. A process for producing a compound claimed in claim 1 carried out substantially as described in any of the foregoing Examples.
8. Compounds claimed in claim 1 when produced by a process as claimed in any of claims 2 to 7.
9. Compounds claimed in claim 1 or 8 and individually identified hereinbefore.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (9)
1. Compounds of the general formula
where R1 denotes linear or branched, unsubstituted or halogen-, alkoxy- or alkylthiosubstituted C1 to C,0 alkyl, R2 denotes linear or branched C1 to C, alkyl or, provided that R' contains 4 or more carbon atoms and/or a halogen, oxygen or sulfur atom, hydrogen, and X denotes halogen.
2. A process for producing a compound as claimed in claim 1, wherein a nitrile oxide of the general formula R1-C=-NO II ee where R1 has the meaning given in claim 1, is reacted with an acetylene compound of the general formula
where R2 and X have the meanings given in claim 1, in the presence or absence of a solvent.
3. A process as claimed in claim 2 carried out at from -20 to +150 C
4. A process as claimed in claim 2 or 3, wherein the nitrile oxide is formed in situ from the corresponding aliphatic nitro compound by elimination of water, or from the corresponding hydroxamic acid halide by dehydrohalogenation.
5. A process as claimed in any of claims 2 to 4, wherein the reaction of the nitrile oxide is carried out in the presence of a tertiary amine to bind hydrogen halide formed.
6. A process as claimed in any of claims 2 to 5, wherein the reaction of the nitrile oxide is carried out in the presence of excess acetylene compound III serving as solvent.
7. A process for producing a compound claimed in claim 1 carried out substantially as described in any of the foregoing Examples.
8. Compounds claimed in claim 1 when produced by a process as claimed in any of claims 2 to 7.
9. Compounds claimed in claim 1 or 8 and individually identified hereinbefore.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752549962 DE2549962A1 (en) | 1975-11-07 | 1975-11-07 | NEW ISOXAZOLES AND THE METHOD OF MANUFACTURING THEM |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1560711A true GB1560711A (en) | 1980-02-06 |
Family
ID=5961145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB45888/76A Expired GB1560711A (en) | 1975-11-07 | 1976-11-04 | Isoxazoles and manufacture thereof |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5259156A (en) |
| BE (1) | BE847919A (en) |
| CH (1) | CH599946A5 (en) |
| DE (1) | DE2549962A1 (en) |
| FR (1) | FR2330685A1 (en) |
| GB (1) | GB1560711A (en) |
| IL (1) | IL50691A (en) |
| IT (1) | IT1121684B (en) |
| NL (1) | NL7612247A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5006515A (en) * | 1987-10-26 | 1991-04-09 | Hoechst Aktiengesellschaft | Pharmaceuticals, phosphorus-containing 2-isoxazolines and isoxazoles contained therein |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2818998A1 (en) * | 1978-04-29 | 1979-11-15 | Basf Ag | 3-ALKYL-5- (2-HYDROXY-STYRYL) -ISOXAZOLES AND METHOD FOR THE PRODUCTION THEREOF |
| DE2943405A1 (en) * | 1979-10-26 | 1981-05-07 | Basf Ag, 6700 Ludwigshafen | NEW AMINO DERIVATIVES OF 5- (2-HYDROXYSTYRYL) -ISOXAZOLE |
| DE3110767A1 (en) * | 1981-03-19 | 1982-09-30 | Basf Ag, 6700 Ludwigshafen | FIGHTING MUSHROOMS WITH 1,2-OXAZOLYLALKYLPHOSPHATES |
| DE3742266A1 (en) * | 1987-12-12 | 1989-06-22 | Basf Ag | 2-TERT.-BUTYL-5-ISOXAZOLYLMETHYLTHIO-3 (2H) -PYRIDAZINE-3-ON DERIVATIVES |
-
1975
- 1975-11-07 DE DE19752549962 patent/DE2549962A1/en not_active Withdrawn
-
1976
- 1976-10-15 IL IL50691A patent/IL50691A/en unknown
- 1976-11-03 CH CH1385376A patent/CH599946A5/xx not_active IP Right Cessation
- 1976-11-03 BE BE172023A patent/BE847919A/en not_active IP Right Cessation
- 1976-11-04 NL NL7612247A patent/NL7612247A/en not_active Application Discontinuation
- 1976-11-04 GB GB45888/76A patent/GB1560711A/en not_active Expired
- 1976-11-05 FR FR7633382A patent/FR2330685A1/en active Granted
- 1976-11-05 IT IT52058/76A patent/IT1121684B/en active
- 1976-11-08 JP JP51133308A patent/JPS5259156A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5006515A (en) * | 1987-10-26 | 1991-04-09 | Hoechst Aktiengesellschaft | Pharmaceuticals, phosphorus-containing 2-isoxazolines and isoxazoles contained therein |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1121684B (en) | 1986-04-10 |
| FR2330685B1 (en) | 1980-04-30 |
| NL7612247A (en) | 1977-05-10 |
| CH599946A5 (en) | 1978-06-15 |
| JPS5259156A (en) | 1977-05-16 |
| IL50691A (en) | 1979-07-25 |
| FR2330685A1 (en) | 1977-06-03 |
| DE2549962A1 (en) | 1977-05-18 |
| BE847919A (en) | 1977-05-03 |
| IL50691A0 (en) | 1976-12-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |