NO783313L - PROCEDURE FOR THE PREPARATION OF 2- (2`, 2`, 2`-TRIBROMETHYL) -4-CHLORICYCLOBUTAN-1-ONER - Google Patents
PROCEDURE FOR THE PREPARATION OF 2- (2`, 2`, 2`-TRIBROMETHYL) -4-CHLORICYCLOBUTAN-1-ONERInfo
- Publication number
- NO783313L NO783313L NO783313A NO783313A NO783313L NO 783313 L NO783313 L NO 783313L NO 783313 A NO783313 A NO 783313A NO 783313 A NO783313 A NO 783313A NO 783313 L NO783313 L NO 783313L
- Authority
- NO
- Norway
- Prior art keywords
- formula
- chlorocyclobutan
- tribromethyl
- carbon atoms
- hydrogen
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 27
- 238000002360 preparation method Methods 0.000 title claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 51
- -1 nitrogen-containing organic bases Chemical class 0.000 claims description 47
- 125000000217 alkyl group Chemical group 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 230000008707 rearrangement Effects 0.000 claims description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 18
- 150000001336 alkenes Chemical class 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- LAGGWVDTBXGDGI-UHFFFAOYSA-N 4,4,4-tribromo-2-chlorobutanoyl chloride Chemical compound ClC(=O)C(Cl)CC(Br)(Br)Br LAGGWVDTBXGDGI-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 150000007513 acids Chemical class 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000007530 organic bases Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 125000005270 trialkylamine group Chemical group 0.000 claims description 7
- FIGVEIIXORGENL-UHFFFAOYSA-N 2-chloro-2-(2,2,2-tribromoethyl)cyclobutan-1-one Chemical compound BrC(CC1(C(CC1)=O)Cl)(Br)Br FIGVEIIXORGENL-UHFFFAOYSA-N 0.000 claims description 6
- PISUDWJJFSQPIN-UHFFFAOYSA-N 2-chloro-4-(2,2,2-tribromoethyl)cyclobutan-1-one Chemical compound ClC1CC(CC(Br)(Br)Br)C1=O PISUDWJJFSQPIN-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- XSGHLZBESSREDT-UHFFFAOYSA-N methylenecyclopropane Chemical compound C=C1CC1 XSGHLZBESSREDT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- SQQWBSBBCSFQGC-JLHYYAGUSA-N ubiquinone-2 Chemical compound COC1=C(OC)C(=O)C(C\C=C(/C)CCC=C(C)C)=C(C)C1=O SQQWBSBBCSFQGC-JLHYYAGUSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 150000004982 aromatic amines Chemical class 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000012442 inert solvent Substances 0.000 claims 1
- 150000003141 primary amines Chemical class 0.000 claims 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims 1
- 150000003335 secondary amines Chemical class 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 239000002585 base Substances 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- HIJYQGOHEVMVFO-UHFFFAOYSA-N 2-(2,2-dibromoethenyl)cyclopropane-1-carboxylic acid Chemical class OC(=O)C1CC1C=C(Br)Br HIJYQGOHEVMVFO-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 7
- 238000007792 addition Methods 0.000 description 7
- NPGZWOXJXVYYFS-UHFFFAOYSA-N 4,4,4-tribromobutanoyl chloride Chemical compound ClC(=O)CCC(Br)(Br)Br NPGZWOXJXVYYFS-UHFFFAOYSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- HBXUQBJHEHAGKF-UHFFFAOYSA-N 4,4,4-tribromobutanoic acid Chemical compound OC(=O)CCC(Br)(Br)Br HBXUQBJHEHAGKF-UHFFFAOYSA-N 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 description 4
- 239000012433 hydrogen halide Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 150000003738 xylenes Chemical class 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 150000004292 cyclic ethers Chemical class 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- KWPQTFXULUUCGD-UHFFFAOYSA-N 3,4,5,7,8,9,10,10a-octahydropyrido[1,2-a][1,4]diazepine Chemical compound C1CCN=CC2CCCCN21 KWPQTFXULUUCGD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-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
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- SHQSVMDWKBRBGB-UHFFFAOYSA-N cyclobutanone Chemical class O=C1CCC1 SHQSVMDWKBRBGB-UHFFFAOYSA-N 0.000 description 2
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- 150000003142 primary aromatic amines Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- 150000003336 secondary aromatic amines Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 229940035637 spectrum-4 Drugs 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 1
- 150000003513 tertiary aromatic amines Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- RYVBINGWVJJDPU-UHFFFAOYSA-M tributyl(hexadecyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC RYVBINGWVJJDPU-UHFFFAOYSA-M 0.000 description 1
- KLBOFRLEHJAXIU-UHFFFAOYSA-N tributylazanium;chloride Chemical compound Cl.CCCCN(CCCC)CCCC KLBOFRLEHJAXIU-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical group CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- NRTLTGGGUQIRRT-UHFFFAOYSA-N triethylazanium;bromide Chemical compound [Br-].CC[NH+](CC)CC NRTLTGGGUQIRRT-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- GNMJFQWRASXXMS-UHFFFAOYSA-M trimethyl(phenyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)C1=CC=CC=C1 GNMJFQWRASXXMS-UHFFFAOYSA-M 0.000 description 1
- VFJYIHQDILEQNR-UHFFFAOYSA-M trimethylsulfanium;iodide Chemical compound [I-].C[S+](C)C VFJYIHQDILEQNR-UHFFFAOYSA-M 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Foreliggende oppfinnelse vedrører en forbedring og videre utformning av fremgangsmåten ved fremstilling av 2- (21 2152'-tri-halogenetyl)-4-halogencyklobutan-l-oner ifølge Søkerens norske patentansøkning nr. 78.1112 av 3o.3.1978. The present invention relates to an improvement and further design of the method for the production of 2-(21 2152'-tri-halogenethyl)-4-halocyclobutan-1-ones according to the Applicant's Norwegian patent application no. 78.1112 of 30.3.1978.
Foreliggende oppfinnelse vedrører videre de ved den forbedrete fremgangsmåte fremstillbare, nye 2-(2'^ 2' 2'-trihalogenetyl)-4-halogencyklobutan-l-oner, såvel nye mellomprodukter som kan anvendes for fremstilling derav. The present invention further relates to the new 2-(2'^2'2'-trihalogenethyl)-4-halocyclobutan-1-ones which can be produced by the improved method, as well as new intermediates which can be used for their production.
Ifølge den fremgangsmåten som er åpenbart i forannevnte patent-ansøkning kan 2-(2'^ 2 '.} 2 -trihalogenetyl)-4-halogen-cyklobutan-l-oner med formelen I According to the method which is obvious in the aforementioned patent application, 2-(2'^2'.}2-trihaloethyl)-4-halo-cyclobutan-1-ones of the formula I
hvor en av restene R-^og R2betyr metyl og den andre hydrogen eller metyl., eller R-^og R2tilsammen en alkylengruppe med 2 til 4 karbonatomer, og X og Y hver er klor eller brom, hvor dog, where one of the residues R-^ and R 2 means methyl and the other hydrogen or methyl., or R-^ and R 2 together an alkylene group with 2 to 4 carbon atoms, and X and Y are each chlorine or bromine, where, however,
når X er brom, må Y alltid likeledes være brom. when X is bromine, Y must also always be bromine.
Forbedringen og den videre utformning av denne fremgangsmåten består ifølge foreliggende oppfinnelse i fremskaffelsen av en fremgangsmåte ved fremstilling av 2-(2',2<1>,2<1->tribrometyl)-4-klorcyklobutan-l-oner med formelen Ia The improvement and further design of this method consists, according to the present invention, in the provision of a method for the production of 2-(2',2<1>,2<1->tribromethyl)-4-chlorocyclobutan-1-ones with the formula Ia
I IN
hvor en av restene R1og R2betyr metyl og den andre hydrogen eller metyl eller R-^og R2tilsammen en alkylengruppe med 2 til 4 karbonatomer. 2-(2',2',2'-tribrometyl)4-klorcyklobutan-l-onene med formel Ia er verdifulle mellomprodukter som i likhet med de ifølge fremgangsmåten ved forannevnte ansøkning fremstillbare 2-(2<1>,2',2'-tribrometyl)-4-bromcyklobutan-l-oner med formelen I kan overføres ved oppvarmning med baser, som alkalimetallhydroksyder og alkalimetallalko-holater, på kjent måte (Favorski-reaksjon) i 2-(2<*>2' dibrom-vinyl)-cyklopropan-l-karbonsyrer henholdsvis deres estere, som på sin side ved den videre omsetning med egnete alkoholer, f. eks. m-fenoksy-a-cyanobenzylalkohol, går over i insekticid virksomme estere. 2-(2<1>,2',2'-tribrometyl)-4-klorcyklobutan-l-oner med formelen Ia kan dog erholdes i vesentlig bedre utbytte enn de tilsvarende 2-(2',2',2'-tribrometyl)-4-bromcyklobutan-l-oner med formel I. Derfor er også 2-(2',2'— dibromvinyl)-cyklo-propan-l-karbonsyrer og deres insekticid virksomme estere lette-re tilgjengelige over de ifølge oppfinnelsen fremstillbare 2-(2<1>,2',2<1->tribrometyl-4-klorcyklobutanl-loner med formelen Ia i bedre utbytte enn over 2-(2<1>,2<1>,2'-tribrometyl)-4-bromcyklo-butan-l-onene med formel I. Insekticid virksomme 2-(2',2'-dibromvinyl)-cyklopropan-l-karbonsyreestere er f.eks. beskrevet i DOS 2.326.077 og 2.439.177. 2-(2',2',2'-tribrometyl)-4-klorcyklobutan-l-onene med formelen Ia fremstilles ifølge foreliggende oppfinnelse på den måte at man omsetter 2-klor-4,4,4-tribromsmørsyreklorid med formelen II I I i nærvær av en organisk base med et olefin med formelen III where one of the radicals R 1 and R 2 means methyl and the other hydrogen or methyl or R 1 and R 2 together an alkylene group with 2 to 4 carbon atoms. The 2-(2',2',2'-tribromethyl)4-chlorocyclobutan-1-ones of formula Ia are valuable intermediates which, like the 2-(2<1>,2',2 '-tribromethyl)-4-bromocyclobutan-1-ones of the formula I can be transferred by heating with bases, such as alkali metal hydroxides and alkali metal alcohols, in a known manner (Favorski reaction) in 2-(2<*>2' dibromo-vinyl )-cyclopropane-1-carboxylic acids or their esters, which in turn by further reaction with suitable alcohols, e.g. m-phenoxy-a-cyanobenzyl alcohol, turns into insecticide-active esters. 2-(2<1>,2',2'-tribromethyl)-4-chlorocyclobutan-1-ones with the formula Ia can, however, be obtained in significantly better yields than the corresponding 2-(2',2',2'-tribromethyl )-4-bromocyclobutan-1-ones with formula I. Therefore, 2-(2',2'-dibromovinyl)-cyclopropane-1-carboxylic acids and their insecticidally active esters are also more readily available than the 2 that can be prepared according to the invention -(2<1>,2',2<1->tribromethyl-4-chlorocyclobutan-lones with the formula Ia in better yield than above 2-(2<1>,2<1>,2'-tribromethyl)-4 -bromocyclo-butan-1-ones of formula I. Insecticidally active 2-(2',2'-dibromovinyl)-cyclopropane-1-carboxylic acid esters are, for example, described in DOS 2,326,077 and 2,439,177. The 2',2',2'-tribromethyl)-4-chlorocyclobutan-1-ones of the formula Ia are prepared according to the present invention by reacting 2-chloro-4,4,4-tribromobutyric acid chloride of the formula II I I in the presence of an organic base with an olefin of formula III
hvor og R2har den under formel I angitte betydning, til where and R2 has the meaning given under formula I, to
et 2-(2',2<1>,2<1->tribrometyl)-2-klorcyklobutan-l-on med formelen a 2-(2',2<1>,2<1->tribromethyl)-2-chlorocyclobutan-1-one of the formula
IV IV
hvor R-^ og R2har den'under formel I angitte betydning, og deretter omleirer dette i nærvær av en katalysator i et 2-(2<1>,2',2<1->tribrometyl)-4-klorcyklobutan-l-on med formelen I. where R-1 and R2 have the meaning given under formula I, and then rearranges this in the presence of a catalyst in a 2-(2<1>,2',2<1->tribromethyl)-4-chlorocyclobutane-1- on with the formula I.
2-klor-4,4,4-tribromsmørsyrekloridet med formel II er en ny forbindelse. Det kan fremstilles idet man først overfører 4,4,4-tribromsmørsyre ved omsetning med et uorganisk syreklorid i 4,4,4-tribromsmørsyreklorid og deretter klorerer dette i ct-stilling. The 2-chloro-4,4,4-tribromobutyric acid chloride of formula II is a new compound. It can be prepared by first transferring 4,4,4-tribromobutyric acid by reaction with an inorganic acid chloride into 4,4,4-tribromobutyric acid chloride and then chlorinating this in the ct position.
Det som utgangsmateriale nødvendige 4,4,4-tribromsmørsyre kan erholdes ved omsetning av bromoform med akrylonitril og etter-følgende hydrolyse av det dannete 4,4,4—tribromsmørsyrenitril The 4,4,4-tribromobutyric acid required as starting material can be obtained by reacting bromoform with acrylonitrile and subsequent hydrolysis of the formed 4,4,4-tribromobutyric acid nitrile
(J.Amer.Chem.Soc. 67, 601-602 (1945)). (J. Amer. Chem. Soc. 67, 601-602 (1945)).
Som uorganiske syreklorider kan anvendes fosfortriklorid, fos-foroksyklorid, fosgen, tionylklorid og oksalylklorid. Omsetningen av 4,4,4-tribromsmørsyre med det uorganiske syreklorid utføres med fordel i nærvær av en katalytisk mengde dimetylformamid. Som løsningsmiddel kan tjene et overskudd av uorganisk syreklorid. As inorganic acid chlorides, phosphorus trichloride, phosphorus oxychloride, phosgene, thionyl chloride and oxalyl chloride can be used. The reaction of 4,4,4-tribromobutyric acid with the inorganic acid chloride is advantageously carried out in the presence of a catalytic amount of dimethylformamide. An excess of inorganic acid chloride can serve as a solvent.
Kloreringen av 4,4,4-tribromsmørsyrekloridet i 2-stilling gjen-nomføres på vanlig måte. Som kloreringsmiddel kan f.eks. anvendes fritt klor eller N-klorsuccinimid. Et foretrukket klore- The chlorination of the 4,4,4-tribromobutyric acid chloride in the 2-position is carried out in the usual way. As a chlorinating agent, e.g. free chlorine or N-chlorosuccinimide is used. A preferred chlorine-
I I I I
ringsmiddel er N-klorsuccinimid. Kloreringen kan gjennomføres' uten isolering av A,4,4-tribromsmørsyrekloridet umiddelbart etter omsetningen av 4,4,4-tribromsmørsyre med det uorganiske syreklorid i overskytende uorganisk syreklorid som løsnings-middel. Man får dog et renere produkt når man isolerer 4,4,4-tribromsmørsyrekloridet og etterpå utfører kloreringen separat. Kloreringen utføres ved en temperatur fra 40 til 90°C, fortrinnsvis 60 til 70°C. Det er fordelaktig å bestråle reaksjonsblandingen under kloreringen med UV-lys eller tilsette noen kjente radikalstarter, f.eks. dibenzoylperoksyd eller azobisisobuty-ronitril. ringing agent is N-chlorosuccinimide. The chlorination can be carried out without isolating the A,4,4-tribromobutyric acid chloride immediately after the reaction of 4,4,4-tribromobutyric acid with the inorganic acid chloride in excess inorganic acid chloride as solvent. However, a cleaner product is obtained when the 4,4,4-tribromobutyric acid chloride is isolated and afterwards the chlorination is carried out separately. The chlorination is carried out at a temperature from 40 to 90°C, preferably 60 to 70°C. It is advantageous to irradiate the reaction mixture during the chlorination with UV light or to add some known radical initiators, e.g. dibenzoyl peroxide or azobisisobutyronitrile.
Omsetningen.av 2-klor-4,4,4-tribromsmørsyreklorid med formelen II med olefiner med formelen III foretas fordelaktig i nærvær av et inert, organisk løsningsmiddel. Egnete sådanne er f.eks. eventuelt halogenerte aromatiske eller alifatiske hydrokarboner, som benzen, toluen, xylener, klorbenzen, diklor- og triklorbenzener, n-pentan, n-heksan, n-oktan, metylenklorid, kloroform, karbontetraklorid, 1,1,2,2-tetrakloretan og trikloretylen. Ytterligere egnete løsningsmidler er cykloalifatiske hydrokarboner, som cyklopentan eller cykloheksan, cykloalifatiske ketoner, som cyklopentanon og cykloheksanon, samt alifatiske ketoner, alifatiske og cykliske etere, alkylnitriler og 3-alkoksypropionitriler med 1 eller 2 karbonatomer i alkoksy-gruppen, spesielt acetonitril og 3-metoksypropionitril. The reaction of 2-chloro-4,4,4-tribromobutyric acid chloride of the formula II with olefins of the formula III is advantageously carried out in the presence of an inert, organic solvent. Suitable such are e.g. optionally halogenated aromatic or aliphatic hydrocarbons, such as benzene, toluene, xylenes, chlorobenzene, dichloro- and trichlorobenzenes, n-pentane, n-hexane, n-octane, methylene chloride, chloroform, carbon tetrachloride, 1,1,2,2-tetrachloroethane and trichloroethylene . Further suitable solvents are cycloaliphatic hydrocarbons, such as cyclopentane or cyclohexane, cycloaliphatic ketones, such as cyclopentanone and cyclohexanone, as well as aliphatic ketones, aliphatic and cyclic ethers, alkylnitriles and 3-alkoxypropionitrile with 1 or 2 carbon atoms in the alkoxy group, especially acetonitrile and 3-methoxypropionitrile .
Spesielt egnete løsningsmidler er alifatiske, cykloalifatiske og aromatiske hydrokarboner, frem for alt alkaner med 5 til 8 karbonatomer, benzen og toluen og spesielt n-heksan og cykloheksan. Particularly suitable solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons, above all alkanes with 5 to 8 carbon atoms, benzene and toluene and especially n-hexane and cyclohexane.
Som løsningsmiddel kan dog også overskytende olefin med formelen III anvendes. As a solvent, however, excess olefin with the formula III can also be used.
Egnete organiske baser i hvis nærvær omsetningen av 2-klor-4,4,4-tribromsmørsyrekloridet med formelen II utføres med et olefin med formelen III, er eksempelvis tertiære aminer, frem for alt trialkylaminer med hver 1 til 4 karbonatomer, spesielt 2 til 4 karbonatomer^i alkylgruppene, cykloske aminer, som Suitable organic bases in the presence of which the reaction of the 2-chloro-4,4,4-tribromobutyric acid chloride of the formula II is carried out with an olefin of the formula III are, for example, tertiary amines, above all trialkylamines each having 1 to 4 carbon atoms, especially 2 to 4 carbon atoms^in the alkyl groups, cyclic amines, which
i pyridin, kinolin, N-alkyl-pyrrolidiner, N-alkyl-piperidiner, in pyridine, quinoline, N-alkyl-pyrrolidines, N-alkyl-piperidines,
N,N-dialkyl-piperaziner og N-alkylmorfoliner eller dialkylani-liner med 1 eller 2 karbonatomer i alkylgruppene, som N-metyl-pyrrolidin, N-etyl-piperidin, N^N<1->dimetyl-piperazin, N-etyl-morfolin og N,N-dimetylanilin, samt bicykliske amidiner, som 1,5-diazabicyklo[5.4.0]undec-5-en og 1,5-diazabicyklo[4.3.0]-non-5-en, og bicykliske diaminer som 1,4-diazabicyklo[2.2.2]-oktan. N,N-dialkyl-piperazines and N-alkylmorpholines or dialkylanilines with 1 or 2 carbon atoms in the alkyl groups, such as N-methyl-pyrrolidine, N-ethyl-piperidine, N^N<1->dimethyl-piperazine, N-ethyl -morpholine and N,N-dimethylaniline, as well as bicyclic amidines, such as 1,5-diazabicyclo[5.4.0]undec-5-ene and 1,5-diazabicyclo[4.3.0]-non-5-ene, and bicyclic diamines as 1,4-diazabicyclo[2.2.2]-octane.
Omsetningen av 2-klor-4,4,4-tribromsmørsyrekloridet med formelen II med olefiner med formelen III utføres fortrinnsvis i nærvær av trialkylaminer med 1 til 4 karbonatomer i alkylgruppene. Spesielt egnete baser er trietylåmin og pyridin. The reaction of the 2-chloro-4,4,4-tribromobutyric acid chloride of the formula II with olefins of the formula III is preferably carried out in the presence of trialkylamines with 1 to 4 carbon atoms in the alkyl groups. Particularly suitable bases are triethylamine and pyridine.
Den organiske base anvendes i minst ekvimolar mengde eller i et lite overskudd med hensyn til 2-klor-4,4,4-tribromsmørsyre-kloridet med formel II. The organic base is used in at least an equimolar amount or in a small excess with respect to the 2-chloro-4,4,4-tribromobutyric acid chloride of formula II.
Olefinene med formelen III anvendes likeledes i minst ekvimolar mengde med hensyn til 2-klor-4,4,4-tribromsmørsyrekloridet med formelen II. Det er dog generelt fordelaktig å anvende et overskudd av olefin, hvorved olefinet, som allerede nevnt, også kan tjene som løsningsmiddel. Ved anvendelse av svakt flyktige olefiner kan reaksjonen utføres under trykk. The olefins of the formula III are likewise used in at least an equimolar amount with respect to the 2-chloro-4,4,4-tribromobutyric acid chloride of the formula II. However, it is generally advantageous to use an excess of olefin, whereby the olefin, as already mentioned, can also serve as a solvent. When using slightly volatile olefins, the reaction can be carried out under pressure.
Som olefiner med formelen III kommer spesielt de i betraktning, i hvilke en av restene R, og R2betyr metyl og den andre hydrogen eller metyl, eller R-^og R2tilsammen betyr en alkylengruppe med 2 til 3 karbonatomer, nemlig isobutylen, propen, metylencyklopropan og metylencyklobutan. Særlig foretrukket er isobutylen og metylencyklopropan. As olefins of the formula III, those in which one of the radicals R, and R2 means methyl and the other hydrogen or methyl, or R-^ and R2 together mean an alkylene group with 2 to 3 carbon atoms, namely isobutylene, propene, methylenecyclopropane and methylenecyclobutane. Particularly preferred are isobutylene and methylenecyclopropane.
Reaksjonstemperaturene kan varieres innen for vie grenser. De ligger i alminnelighet mellom 0 og 200°C, fortrinnsvis mellom 20 og 160°C. The reaction temperatures can be varied within wide limits. They are generally between 0 and 200°C, preferably between 20 and 160°C.
2-(2,2',2<1->tribrometyl)-2-klorcyklobutan-l-onene med formelen IV er likeledes nye forbindelser. The 2-(2,2',2<1->tribromethyl)-2-chlorocyclobutan-1-ones of the formula IV are also new compounds.
i in
j j
1 1
Som katalysatorer for omleiringen av de først erholdte 2-(2 2 2 '-tribrometyl).-2-klorcyklobutan-loner med formelen IV i 2-(2',2<1>,2'-tribrometyl)-4-klorcyklobutan-l-oner med formelen I kan anvendes syrer, baser eller kvaternære ammoniumhalogenider. As catalysts for the rearrangement of the first obtained 2-(2 2 2 '-tribromethyl).-2-chlorocyclobutanes of the formula IV in 2-(2',2<1>,2'-tribromethyl)-4-chlorocyclobutane- Ions with the formula I can be used acids, bases or quaternary ammonium halides.
Omleiringen ifølge oppfinnelsen av 2-(2',2',2'-tribrometyl)-2-klorcyklobutan-l-oner med- formelen IV til 2-(2',2',2<1->tribrom-etyl) -4-klorcyklobutan-l-oner med formelen I er uventet og ikke kjent hos cyklobutanoner som er monohalogenerte i a-stilling. Omleiringen forløper i utmerket, ofte kvantitativt utbytte. The rearrangement according to the invention of 2-(2',2',2'-tribromomethyl)-2-chlorocyclobutan-1-ones with the formula IV to 2-(2',2',2<1->tribromo-ethyl)- 4-chlorocyclobutan-1-ones of the formula I are unexpected and not known in cyclobutanones which are monohalogenated in the a-position. The resettlement proceeds with excellent, often quantitative results.
Omleringen ifølge oppfinnelsen av 2-(2',2',2'-tribrometyl)-2-klorcyklobutan-l-oner med formel IV i 2-(2<1>,2<1>,2<1->tribrometyl)-4-klorcyklobutan-l-oner med formelen I utføres fortrinnsvis i nærvær av basiske katalysatorer. Som basiske katalysatorer kommer organiske baser i betraktning, som primære, sekundære og spesielt tertiære aminer med formelen The rearrangement according to the invention of 2-(2',2',2'-tribromethyl)-2-chlorocyclobutan-1-ones of formula IV in 2-(2<1>,2<1>,2<1->tribromethyl) -4-chlorocyclobutan-1-ones of the formula I are preferably carried out in the presence of basic catalysts. As basic catalysts, organic bases come into consideration, such as primary, secondary and especially tertiary amines with the formula
hvor Q betyr alkyl med 1 til 8 karbonatomer, cykloalkyl med 5 til 6 karbonatomer, benzyl eller fenyl og Q2og Q2uavhengig where Q means alkyl with 1 to 8 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, benzyl or phenyl and Q 2 and Q 2 are independent
av hverandre betyr hydrogen eller alkyl med 1 til 8 karbonatomer. Egnete basiske katalysatorer er f.eks. trietylamin, tri-n-butylamin, tri-isopentylamin, tri-n-oktylamin, N,N-dimetyl-cykloheksylamin, N,N-dimetylbenzylamin, N,N-dimetyl-2-etylhek-sylamin, N,N-dietylanilin, såvel som ytterligere cykliske aminer, som pyridin, kinolin, lutidin, N-alkylmorfoliner, som N-metylmorfoliner, N-alkylpiperidiner, som N-metyl- og N-etyl-piperidin, N-alkylpyrrolidiner som N-metyl- og N-etylpyrrolidin, diaminer, som N,N,N<*>,N'-tetrametyletylendiamin, N,N,N',N'-tetrametyl-1,3-diaminobutan, N,N<1->dialkylpiperaziner som N,N'-dimetylpiperazin, bicykliske aminer, som 1,4-diazabicyklo-[2,2,2]oktan og bicykliske amidiner, som 1,5-diazabicyklo[5.4.0]-undec-5-en og 1,5-diazabicyklo[4.3.0]non-5-en, og endelig polymere basiske forbindelser, som p-dimetylaminometylpolystyren. of each other means hydrogen or alkyl of 1 to 8 carbon atoms. Suitable basic catalysts are e.g. triethylamine, tri-n-butylamine, tri-isopentylamine, tri-n-octylamine, N,N-dimethyl-cyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethyl-2-ethylhexylamine, N,N-diethylaniline, as well as further cyclic amines, such as pyridine, quinoline, lutidine, N-alkylmorpholines, such as N-methylmorpholines, N-alkylpiperidines, such as N-methyl- and N-ethyl-piperidine, N-alkylpyrrolidines such as N-methyl- and N-ethylpyrrolidine , diamines, such as N,N,N<*>,N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-diaminobutane, N,N<1->dialkylpiperazines such as N,N'- dimethylpiperazine, bicyclic amines, such as 1,4-diazabicyclo-[2,2,2]octane and bicyclic amidines, such as 1,5-diazabicyclo[5.4.0]-undec-5-ene and 1,5-diazabicyclo[4.3. 0]non-5-ene, and finally polymeric basic compounds, such as p-dimethylaminomethylpolystyrene.
Videre egnete basiske katalysatorer for omleiringen ifølge oppfinnelsen av et 2-(2<1>,2<1>,2<1->tribrometyl)-2-klorcyklobutan-l-on Furthermore, suitable basic catalysts for the rearrangement according to the invention of a 2-(2<1>,2<1>,2<1->tribromethyl)-2-chlorocyclobutan-1-one
med formel IV i et 2-(2',2',2<1->tribrometyl)-4-klorcyklobutan-1-on med formel I er fosfiner, spesielt trialkylfosfiner, eksempelvis tributylfosfin. with formula IV in a 2-(2',2',2<1->tribromethyl)-4-chlorocyclobutan-1-one with formula I are phosphines, especially trialkylphosphines, for example tributylphosphine.
Som sure katalysatorer for omleiringen av 2-(2<1>,2<1>,2'-tribrom-etyl) -2-klorcyklobutan-l-oner med formelen IV i tribrometyl-klorcyklobutan-l-oner med formelen I kan anvendes uorganiske eller organiske protonsyrer. Egnete uorganiske protonsyrer er eksempelvis hydrogenhalogenidsyrer, som hydrogenklorid, hydrogen-bromid, hydrogenfluorid og hydrogenjodid, salpetersyre, fosforsyre og svovelsyre. Foretrukné uorganiske protonsyrer er hydrogenhalogenidsyrer . As acid catalysts for the rearrangement of 2-(2<1>,2<1>,2'-tribromoethyl)-2-chlorocyclobutan-1-ones of the formula IV into tribromethyl-chlorocyclobutan-1-ones of the formula I can be used inorganic or organic protonic acids. Suitable inorganic protonic acids are, for example, hydrogen halide acids, such as hydrogen chloride, hydrogen bromide, hydrogen fluoride and hydrogen iodide, nitric acid, phosphoric acid and sulfuric acid. Preferred inorganic protonic acids are hydrohalic acids.
Anvendes syrer eller baser i overskudd så kan de også tjene som løsningsmiddel. If acids or bases are used in excess, they can also serve as solvents.
Videre kan salter av protonsyrer, spesielt hydrogenhalogenidsyrer, med ammoniakk eller en nitrogenholdig organisk base samt kvaternære ammoniumhalogenider, kvaternære fosfoniumhalogenider og sulfoniumhalogenider anvendes. Egnete nitrogenholdige organiske baser er alifatiske, cykloalifatiske, aralifatiske og aromatiske primære, sekundære og tertiære aminer samt heterocykliske nitrogenbaser. Som eksempler kan nevnes: primære alifatiske aminer med opp til 12 C-atomer, som metylamin, etylamin, n-butylamin, n-oktylamin, n-dodecylamin, heksametylendiamin, cyklohek-sylamin, benzylamin; sekundære alifatiske aminer med opp til 12 C-atomer, som dimetylamin, dietylamin, di-n-propylamin, dicyklo-heksylamin, pyrrolidin, piperidin, piperazin, morfolin; tertiære alifatiske aminer særlig trialkylaminer 1 til 4 C-atomer i hver alkyldel, som trietylamin, tri-n-butylamin, N-metylpyrrolidin^N-metylmorfolin, 1,4-diazabicyklo[2,2,2]oktan, chinuklidin; eventuelt substituerte primære, sekundære og tertiære aromatiske aminer, som anilin, toluidin, naftylamin, N-metylanilin, di-fenylamin og N,N-dietylanilin, videre pyridin, pikolin, indolin og kinolin. Furthermore, salts of protonic acids, especially hydrogen halide acids, with ammonia or a nitrogen-containing organic base as well as quaternary ammonium halides, quaternary phosphonium halides and sulfonium halides can be used. Suitable nitrogen-containing organic bases are aliphatic, cycloaliphatic, araliphatic and aromatic primary, secondary and tertiary amines as well as heterocyclic nitrogen bases. Examples may be mentioned: primary aliphatic amines with up to 12 C atoms, such as methylamine, ethylamine, n-butylamine, n-octylamine, n-dodecylamine, hexamethylenediamine, cyclohexylamine, benzylamine; secondary aliphatic amines with up to 12 C atoms, such as dimethylamine, diethylamine, di-n-propylamine, dicyclohexylamine, pyrrolidine, piperidine, piperazine, morpholine; tertiary aliphatic amines especially trialkylamines 1 to 4 C atoms in each alkyl part, such as triethylamine, tri-n-butylamine, N-methylpyrrolidine^N-methylmorpholine, 1,4-diazabicyclo[2,2,2]octane, quinuclidine; optionally substituted primary, secondary and tertiary aromatic amines, such as aniline, toluidine, naphthylamine, N-methylaniline, di-phenylamine and N,N-diethylaniline, further pyridine, picoline, indoline and quinoline.
I 1<1>Som kvartære fosfoniumhalogenider kommer f.eks. i betraktning: heksadecyltributylfosfoniumbromid, metyl- og etyl-tri-fenyl-fosfoniumbromid; som sulfoniumhalogenid, f.eks. trimetylsul-foniumjodid. In 1<1>As quaternary phosphonium halides, e.g. in consideration: hexadecyltributylphosphonium bromide, methyl- and ethyl-tri-phenyl-phosphonium bromide; as sulfonium halide, e.g. trimethylsulfonium iodide.
Foretrukket er salter med formelen Salts with the formula are preferred
hvor M betyr fluor, brom eller jod, spesielt klor, where M means fluorine, bromine or iodine, especially chlorine,
Q4hydrogen, alkyl med 1-18 C-atomer, cykloheksyl, benzyl, fenyl eller naftyl og Q4hydrogen, alkyl with 1-18 C atoms, cyclohexyl, benzyl, phenyl or naphthyl and
Q5, Qg og Q7uavhengig av hverandre hydrogen eller alkyl med 1-18 C-atomer, Q5, Qg and Q7 independently of each other hydrogen or alkyl with 1-18 C atoms,
samt N-alkyl-pyridiniumhalogenider med 1-18 C-atomer i alkylet, spesielt i de tilsvarende klorider. as well as N-alkyl pyridinium halides with 1-18 C atoms in the alkyl, especially in the corresponding chlorides.
Eksempler på slike salter er: ammoniumklorid, ammoniumbromid, metylaminhydroklorid, cykloheksylaminhydroklorid, anilinhydro-klorid, dimetylaminhydroklorid, di-isobutylaminohydroklorid, trietylaminhydroklroid, trietylaminhydrobromid, tri-n-oktyl-aminhydroklorid, benzyl-dimetylaminhydroklorid, tetrametyl-, tetraetyl-, tetra-n-propyl-, tetra-n-butylammoniumklorid, -bro-mid og -jodid, trimetyl-heksadecylammoniumklorid, benzyldimetyl-heksadecylammoniumklroid, benzyldimetyltetradecyklammoniumklorid, benzyl-trimetyl-, trietyl- og tri-n-butylammoniumklorid, n-bu^tyl-tri-n-propylaramoniumbromid, oktadecy 1 trimety 1 ammoniumbromid, fenyltrimetylammoniumbromid eller -klorid, heksadecylpyridinium-brom og -klorid. Examples of such salts are: ammonium chloride, ammonium bromide, methylamine hydrochloride, cyclohexylamine hydrochloride, aniline hydrochloride, dimethylamine hydrochloride, di-isobutylamino hydrochloride, triethylamine hydrochloride, triethylamine hydrobromide, tri-n-octylamine hydrochloride, benzyl-dimethylamine hydrochloride, tetramethyl-, tetraethyl-, tetra-n- propyl-, tetra-n-butylammonium chloride, -bromide and -iodide, trimethyl-hexadecylammonium chloride, benzyldimethyl-hexadecylammonium chloride, benzyldimethyltetradecylammonium chloride, benzyl-trimethyl-, triethyl- and tri-n-butylammonium chloride, n-bu^tyl-tri-n -propylarammonium bromide, octadecy 1 trimethy 1 ammonium bromide, phenyltrimethylammonium bromide or chloride, hexadecylpyridinium bromide and chloride.
Som.ytterligere ko-katalysatorer kan man anvende alkalimetall-halogenider som kaliumjodid, natriumjodid, litiumjodid, kalium-broraid, natriumbromid, litiumbromid, kaliumklorid, natriumklo-rid, litiumklorid, kaliumfluorid, natriumfluorid og litium-fluorid. Alkali metal halides such as potassium iodide, sodium iodide, lithium iodide, potassium bromide, sodium bromide, lithium bromide, potassium chloride, sodium chloride, lithium chloride, potassium fluoride, sodium fluoride and lithium fluoride can be used as further co-catalysts.
Disse ko-katalysatorer katalyserer reaksjonen også i fravær "av ovennevnte ammoniumsalter, dog er da tilsetninger av åpen-! kjedete eller makrocykliske polyestere (krone-etere) fordelaktig for raskt forløp. Eksempler på slike krone-etere er: 15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicykloheksyl-18-crown-6, 5,6,14,15-dibenzo-7,13-diaza-l,4-dioksa-cyklopenta-deka-5,14-dien. These co-catalysts catalyze the reaction also in the absence of the above-mentioned ammonium salts, however, then additions of open-chain or macrocyclic polyesters (crown ethers) are advantageous for rapid progress. Examples of such crown ethers are: 15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, 5,6,14,15-dibenzo-7,13-diaza-1,4-dioxa-cyclopenta-deca-5, the 14th.
Mengden av anvendt katalysator kan variere innen vide grenser. I mange tilfeller er det tilstrekkelig når katalysatoren fore-ligger i spor. Generelt anvendes katalysatoren dog foretrukket i en mengde på ca. 0,1 til 15 vekts%, beregnet på forbindelsen med formel VI. The amount of catalyst used can vary within wide limits. In many cases, it is sufficient when the catalyst is present in traces. In general, however, the catalyst is preferably used in an amount of approx. 0.1 to 15% by weight, calculated on the compound of formula VI.
Omleiringen kan foretas både i smelte og i et inert organisk løsningsmiddel. The redeposition can be carried out both in melt and in an inert organic solvent.
Reaksjonstemperaturene for omleiringen i smeiten ligger i alminnelighet mellom 60 og 150°C, spesielt 80 og 130°C. The reaction temperatures for the rearrangement in the smelting are generally between 60 and 150°C, especially 80 and 130°C.
For omleiringen i smeiten er egnete katalysatorer frem for alt de foran nevnte organiske baser, spesielt trialkylaminer med 1-8 C-atomer i hver alkyldel, videre salter av hydrogenhalogenidsyrer med ammoniakk eller organiske nitrogenholdige baser, som trialkylaminhydroklorider og -bromider med 1-8 C-atomer i hver alkyldel, og helt spesielt tetraalkylammoniumhalogenider, frem for alt -klorider, -bromider og -jodider med 1-18 C-atomer i hver alkyldel. For the rearrangement in the smelting, suitable catalysts are above all the aforementioned organic bases, especially trialkylamines with 1-8 C atoms in each alkyl part, further salts of hydrogen halide acids with ammonia or organic nitrogen-containing bases, such as trialkylamine hydrochlorides and bromides with 1-8 C -atoms in each alkyl part, and especially tetraalkylammonium halides, above all -chlorides, -bromides and -iodides with 1-18 C atoms in each alkyl part.
Egnete inerte organiske løsningsmidler er f.eks. Suitable inert organic solvents are e.g.
- eventuelt nitrerte eller halogenerte alifatiske, cykloalifatiske eller aromatiske hydrokarboner, som n-heksan, n-pentan, cykloheksan, benzen, toluen, xylener, nitrobenzen, kloroform, karbontetraklorid, trikloretylen, 1,1,2,2-tetrakloretan, nitro-metan, klorbenzen, diklorbenzener og triklorbenzener; - lavere alifatiske alkoholer, f.eks. slite med opp til 6 C-atomer, som metanol etanol, propanol, isopropanol, butanoler og pentanoler; I - alifatiske dioler, som etylenglykol og dietylenglykol: - etylenglykolmo.noalkyleter og dietylenglykolmonoalkyleter med 1-4 C-atomer i hver alkyldel, som etylenglykolmonometyl-og -monoetyleter, dietylenglykolmonometyl- og -monoetyleter; - cyklikske a ider, som N-metyl-2-pyrrolidon, N-acetyl-2-pyrro-lidon og N-metyl-£-kaprolaktam; -amider av kullsyre, som tetrametylurea og dimorfolinkarbonyl; - amider av fosforsyrling>fosforsyre, fenylfosfonsyre eller av alifatiske fosfonsyrer med 1-3 C-atomer i syredelen, som.fos-forsyretriamid, fosforsyretris(dimetylamid), fosforsyretrimor-folid, fosforsyretripyrrolinid, fosforsyre-bis(dimetylamid)-morfolid, fosforsyre-dimetylamid-dietylamid-morfolid, fosforsyrling-tris(dimetylamid), tetrametyldiamid av metanfosfonsyre; - amider av svovelsyre, av alifatiske eller aromatiske sulfonsyrer, som tetrametylsulfamid, dimetylamid av metansulfonsyre eller p-toluensulfonsyreamid; - svovelholdige løsningsmidler, som organiske sulfoner og sulf-oksyder, f.eks. dimetylsulfoksyd og sulfolan; - alifatiske og aromatiske nitriler, 3-alkoksypropionitriler, alifatiske ketoner, alkyl- og alkoksyalkylestere av alifatiske monokarbonsyrer, cykloske etere, dialkyleter, N,N-disubstituerte amider av alifatiske monokarbonsyrer og etylenglykol- og diety-lenglykoldialkyleter av den under fremgangsmåtetrinn 1) - optionally nitrated or halogenated aliphatic, cycloaliphatic or aromatic hydrocarbons, such as n-hexane, n-pentane, cyclohexane, benzene, toluene, xylenes, nitrobenzene, chloroform, carbon tetrachloride, trichloroethylene, 1,1,2,2-tetrachloroethane, nitro-methane , chlorobenzene, dichlorobenzenes and trichlorobenzenes; - lower aliphatic alcohols, e.g. struggle with up to 6 C atoms, such as methanol ethanol, propanol, isopropanol, butanols and pentanols; I - aliphatic diols, such as ethylene glycol and diethylene glycol: - ethylene glycol monoalkyl ether and diethylene glycol monoalkyl ether with 1-4 C atoms in each alkyl part, such as ethylene glycol monomethyl and -monoethyl ether, diethylene glycol monomethyl and -monoethyl ether; - cyclic aides, such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-methyl-£-caprolactam; -amides of carbonic acid, such as tetramethylurea and dimorpholinecarbonyl; - amides of phosphoric acid>phosphoric acid, phenylphosphonic acid or of aliphatic phosphonic acids with 1-3 C atoms in the acid part, such as phosphoric acid triamide, phosphoric acid tris(dimethylamide), phosphoric acid trimorfolide, phosphoric acid tripyrrolinide, phosphoric acid bis(dimethylamide)-morpholide, phosphoric acid- dimethylamide-diethylamide-morpholide, phosphoric acid-tris(dimethylamide), tetramethyldiamide of methanephosphonic acid; - amides of sulfuric acid, of aliphatic or aromatic sulfonic acids, such as tetramethylsulfamide, dimethylamide of methanesulfonic acid or p-toluenesulfonic acid amide; - sulphur-containing solvents, such as organic sulphones and sulph-oxides, e.g. dimethyl sulfoxide and sulfolane; - aliphatic and aromatic nitriles, 3-alkoxypropionitriles, aliphatic ketones, alkyl and alkoxyalkyl esters of aliphatic monocarboxylic acids, cyclic ethers, dialkyl ethers, N,N-disubstituted amides of aliphatic monocarboxylic acids and ethylene glycol and diethylene glycol dialkyl ethers of that under method step 1)
nevnte type. said type.
For omleiringen i nærvær av en sur katalysator anvender man med fordel polare løsningsmidler, spesielt lavere alkoholer, som metanol, etanol og butanoler, N,N-dialkylamider av alifatiske monokarbonsyrer med 1-3 C-atomer i syredelen, spesielt N,N-dimetylformamid, eller dialkylsulfoksyder, som dimetylsulfoksyd. For the rearrangement in the presence of an acidic catalyst, polar solvents are advantageously used, especially lower alcohols, such as methanol, ethanol and butanols, N,N-dialkylamides of aliphatic monocarboxylic acids with 1-3 C atoms in the acid part, especially N,N-dimethylformamide , or dialkyl sulfoxides, such as dimethyl sulfoxide.
I aprotiske, sterkt polare løsningsmidler som de forannevnte N,N-disubstituerte amider av alifatiske monokarbonsyrer, cykliske amider, amider av kullsyre, amider av fosforsyrling, fosforsyre, fenylfosfonsyre eller av alifatiske fosfonsyrer, amider av svovelsyre eller av alifatiske eller aromatiske sulfonsyrer, samt dialkylsulfoksyder, som dimetylsulfoksyd, forløper reaksjonen også uten tilsetning av base eller syre. I disse tilfeller virker■løsningsmidlet som katalysator. i In aprotic, strongly polar solvents such as the aforementioned N,N-disubstituted amides of aliphatic monocarboxylic acids, cyclic amides, amides of carbonic acid, amides of phosphoric acid, phosphoric acid, phenylphosphonic acid or of aliphatic phosphonic acids, amides of sulfuric acid or of aliphatic or aromatic sulfonic acids, as well as dialkyl sulfoxides , such as dimethylsulfoxide, the reaction also proceeds without the addition of base or acid. In these cases,■the solvent acts as a catalyst. in
Ii I alminnelighet tilsettes dog ved omleiringen i nærvær av et' Ii In general, however, is added during the rearrangement in the presence of a
inert organisk løsningsmiddel en katalysator, fortrinnsvis en organisk base med en pKa-verdi på over 9, spesielt trialkylaminer med 1-8 C-atomer i alkyldelen, som trietylamin, tri-n-butylamin og tri-n-oktylamin; videre hydrogenhalogenidsyrer, spesielt HC1 og HBr, samt tetraalkylammoniumhalogenider, spesielt -klorider, -bromider og -jodider, med 1-18 C-atomer i alkyldelen. inert organic solvent a catalyst, preferably an organic base with a pKa value above 9, especially trialkylamines with 1-8 C atoms in the alkyl part, such as triethylamine, tri-n-butylamine and tri-n-octylamine; further hydrogen halide acids, especially HC1 and HBr, as well as tetraalkylammonium halides, especially -chlorides, -bromides and -iodides, with 1-18 C atoms in the alkyl part.
Særlig foretrukne løsningsmidler er alifatiske alkoholer med 1- 4 C-atomer, toluen, xylener, klorbenzen, dioksan,.acetonitril, 3-metoksypropionitril, etylenglykoldietyleter og di-isopropyl-keton. Particularly preferred solvents are aliphatic alcohols with 1-4 C atoms, toluene, xylenes, chlorobenzene, dioxane, acetonitrile, 3-methoxypropionitrile, ethylene glycol diethyl ether and diisopropyl ketone.
Reaksjonstemperaturene for omleiringen i nærvær av et inert organisk løsningsmiddel ligger vanligvis mellom ca. 0 og 150°C, fortrinnsvis mellom ca. 80 og 130°C. The reaction temperatures for the rearrangement in the presence of an inert organic solvent are usually between approx. 0 and 150°C, preferably between approx. 80 and 130°C.
Med fremgangsmåten ifølge oppfinnelsen blir nye, i 3-stilling substituerte, som mellomprodukter for fremstillingen av i 3-stilling substituerte 2-(2',2'~——dibromvinyl)-cyklopropankar-bonsyrederivater egnete 2-(2<1>,2',2'-tribrometyl)-4-klorcyklo-butan-l-oner med formel I tilgjengelige ut fra lett tilgjengelige utgangsmaterialer på enkel måte og i godt utbytte. For-løpet av fremgangsmåten ifølge oppfinnelsen er ytterst overra-skende og absolutt ikke å forutse, da det ved omsetningen av 2- klor-4,4,4-tribromsmørsyrekloridet med formel II henh. et derav ved avspaltning av hydrogenklorid in situ dannet klor-keten med et olefin med formelen III først dannes et for den videre omleiring i et i 3-stilling substituert 2-(2',2' —■—di-bromvinyl)-cyklopropankarbonsyrederivat uegnet 2-(2<1>,2',2<1->tri-brometyl) -2-klorcyklobutan-l-on med formelen IV, som så over ved en ny, ved i a-stilling monohalogenerte cyklobutanoner tid-ligere ikke observert omleiring i et for den videre omleiring til et i 3-stilling substituert 2— (2' , 2' dibromvinyl)cyklopro-pankarbonsyre-derivat egnet 2-(2<1>,2',2'-tribrometyl)-4-klor-cyklobutan-l-on med formelen I. With the method according to the invention, new, substituted in the 3-position, as intermediates for the preparation of substituted in the 3-position 2-(2',2'~——dibromovinyl)-cyclopropanecarboxylic acid derivatives 2-(2<1>,2 ',2'-tribromethyl)-4-chlorocyclo-butan-1-ones of formula I accessible from readily available starting materials in a simple manner and in good yield. The course of the method according to the invention is extremely surprising and absolutely not predictable, since in the reaction of the 2-chloro-4,4,4-tribromobutyric acid chloride with formula II acc. one of which by cleavage of hydrogen chloride in situ formed chloroketene with an olefin of the formula III first forms a for the further rearrangement in a 3-position substituted 2-(2',2'-■-dibromovinyl)-cyclopropanecarboxylic acid derivative unsuitable 2-(2<1>,2',2<1->tri-bromomethyl)-2-chlorocyclobutan-1-one of the formula IV, which saw above in a new monohalogenated cyclobutanones in the a-position previously not observed rearrangement in a suitable 2-(2<1>,2',2'-tribromomethyl)-4- chloro-cyclobutan-l-one of the formula I.
I IN
i in
■ De ut fra nye 2-(2<1>,2<1>,2'-tribrometyl)-4-klorcyklobutan-l-oner med formel I fremstillbare, i 3-stilling substituerte 2-(2',2'-dibromvinyl)-cyklopropankarbonsyrer og deres insekticid-virksomme estere kan beskrives ved den etterfølgende formel VIII. ■ The 3-position substituted 2-(2',2'- dibromovinyl) cyclopropane carboxylic acids and their insecticidally active esters can be described by the following formula VIII.
hvor X, og R2 'har de under formel I angitte betydningér, og R er hydrogen, alkyl med 1 til 4 karbonatomer eller en gruppe med formelen IX hvor R^betyr oksygen, svovel eller vinylengruppen, R^hydrogen, alkyl med 1 til 4 karbonatomer, benzyl, fenoksy eller fenyl-merkapto, R^hydrogen eller en alkylgruppe med 1 til 4 karbonatomer og Rg hydrogen, cyano eller etinyl eller, når en av restene R^og R2er metyl og den andre hydrogen eller metyl, er R2 vinylen-gruppen, R^fenoksy og R^hydrogen, også alkyl med 1 til 5 karbonatomer. where X, and R2' have the meanings given under formula I, and R is hydrogen, alkyl with 1 to 4 carbon atoms or a group with the formula IX where R^ means oxygen, sulfur or the vinylene group, R^hydrogen, alkyl with 1 to 4 carbon atoms, benzyl, phenoxy or phenyl-mercapto, R^ hydrogen or an alkyl group of 1 to 4 carbon atoms and R g hydrogen, cyano or ethynyl or, when one of the radicals R^ and R 2 is methyl and the other hydrogen or methyl, R 2 is vinylene- the group, R^phenoxy and R^hydrogen, also alkyl with 1 to 5 carbon atoms.
2-(21,2' dibromviny1)-cyklopropankarbonsyrederivatene med formelen VIII, hvor R betyr en gruppe med formelen.IX, egner seg for bekjempelse av forskjellige dyriske eller vegetabilske skadevesener, spesielt insekter. Egenskaper, anvendelsesområder og anvendelsesformer av disse virkestoffene er beskrevet i lit-teraturen (sml. f.eks. Nature, 246, 169-170 (1973) Nature, 248 710-711 (1974); Proceedings 7th British Insecticide and Fungicide Conference, 721-728 (1973); Proceedings 8th British Insecticide and Fungicide Conference, 373-78 (1975); J. Agr. Food Chem. 23, 115(1973); US patent 3.961.070; DOS 2.553.991, 2.439.177, 2.326.077 og 2.614.648). The 2-(21,2' dibromovinyl)-cyclopropanecarboxylic acid derivatives of the formula VIII, where R represents a group of the formula IX, are suitable for combating various animal or vegetable pests, especially insects. Properties, areas of application and forms of application of these active substances are described in the literature (cf. e.g. Nature, 246, 169-170 (1973) Nature, 248 710-711 (1974); Proceedings 7th British Insecticide and Fungicide Conference, 721 -728 (1973); Proceedings 8th British Insecticide and Fungicide Conference, 373-78 (1975); J. Agr. Food Chem. 23, 115(1973); US patent 3,961,070; DOS 2,553,991, 2,439,177, 2,326,077 and 2,614,648).
ii Overføringen av 2-(2',2<1>,2'-tribrometyl)-4-klor-cyklobutan-l- I oner med formelen I i 2-(2',2' dibromvinyl)-cyklopropan-karbonsyrederivater med formelen VIII skjer på en i og for seg kjent måte ved oppvarmning i nærvær av egnete baser. Egnete baser er eksempelvis alkalimetall- og jordalkalimetallhydroksyder, som natriumhydroksyd, kaliumhydroksyd, kalsiumhydroksyd og ba-riumhydroksyd. Også alkalimetall- og jordalkalimetallkarbonater og -hydrogenkarbonater, som kalsiumkarbonat, bariumkarbonat, kaliumkarbonat, natriumkarbonat, natriumhydrogenkarbonat og ka-liumhydrogenkarbonat kan anvendes som baser. Ytterligere egnet som baser er alkoholater avledet fra resten R ifølge ovennevnte definisjon, spesielt de tilsvarende natrium- og kaliumalkoholater. Anvendelsen av slike alkoholater har den fordel at den tilsvarende ester erholdes umiddelbart, mens ved anvendelse av alkalimetall- og jordalkalimetallhydroksyder erholdes først saltene av disse baser med den dannete 2-(2',2'—— dibromvinyl)-cyklo-propankarbonsyre. Disse kan dog likeledes på enkel og i og for seg kjent måte, f.eks. ved overføring i det tilsvarende syreklorid og omsetning med en alkohol avledet fra resten R?over-føres i estere. ii The conversion of 2-(2',2<1>,2'-tribromomethyl)-4-chloro-cyclobutan-1- Iones of the formula I into 2-(2',2' dibromovinyl)-cyclopropane-carboxylic acid derivatives of the formula VIII takes place in a manner known per se by heating in the presence of suitable bases. Suitable bases are, for example, alkali metal and alkaline earth metal hydroxides, such as sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide. Alkali metal and alkaline earth metal carbonates and hydrogen carbonates, such as calcium carbonate, barium carbonate, potassium carbonate, sodium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate can also be used as bases. Further suitable as bases are alcoholates derived from the radical R according to the above definition, especially the corresponding sodium and potassium alcoholates. The use of such alcoholates has the advantage that the corresponding ester is obtained immediately, while when using alkali metal and alkaline earth metal hydroxides, the salts of these bases are first obtained with the formed 2-(2',2'——dibromovinyl)-cyclopropanecarboxylic acid. However, these can also be done in a simple and per se known manner, e.g. by transfer into the corresponding acid chloride and reaction with an alcohol derived from the residue R? is transferred into esters.
Overføringen av et 2-(2<1>,2<1>,2'-tribrometyl)-4-klor-cyklobutan-1-on med formel I i et 2-(2',2' dibromvinyl)-cyklopropankar-bonsyrederivat med formelen VIII foretas avhengig av typen av anvendt base hensiktsmessig i vandig, vandig-organisk eller organisk medium, Når et alkalimetall- eller jordalkalimetallkarbonat anvendes som base, så utføres omsetningen i vandig eller vandig-organisk medium. Også omsetningen i nærvær av alkalimetall-eller jordalkalimetallhydroksyder og alkalimetallhydrogenkarbo-nater foretas med fordel i vandig eller vandig-organisk medium. Derved erholdes etter surgjøring av reaksjonsblandingen, f.eks. ved tilsetning av konsentrert saltsyre, de frie 2-(2<1>,2'-dibrom-vinyl) -cyklopropankarbonsyrer med formelen VIII (R = H). The conversion of a 2-(2<1>,2<1>,2'-tribromomethyl)-4-chloro-cyclobutan-1-one of formula I into a 2-(2',2' dibromovinyl)-cyclopropanecarboxylic acid derivative with the formula VIII is carried out depending on the type of base used appropriately in an aqueous, aqueous-organic or organic medium. When an alkali metal or alkaline earth metal carbonate is used as base, the reaction is carried out in an aqueous or aqueous-organic medium. The reaction in the presence of alkali metal or alkaline earth metal hydroxides and alkali metal hydrogen carbonates is also advantageously carried out in an aqueous or aqueous-organic medium. Thereby, after acidifying the reaction mixture, e.g. by addition of concentrated hydrochloric acid, the free 2-(2<1>,2'-dibromo-vinyl)-cyclopropanecarboxylic acids of the formula VIII (R = H).
Egnete løsningsmidler for omsetningen av 2-(2<1>,2<1>,2<1->tribrom-etyl) -4-klorcyklobutan-l-oner med formelen I i 2-(2<1>,2<1->dibrom-vinyl) -cyklopropankarbonsyrederivater med formelen VIII i vandig-organisk eller organisk medium er lavere alkoholer, f.eks. slike med 1 til 6 karbonatomer, benzylalkohol, alifatiske eller cykliske etere, som dietyleter, di-n-propyleter, di-isopropyl-l eter, tetrahydrofuran og dioksan, samt alifatiske, cykloalifa-.tiske eller aromatiske hydrokarboner, som n-pentan, n-heksan, cykloheksan, benzen, toluen og xylener. Suitable solvents for the reaction of 2-(2<1>,2<1>,2<1->tribromoethyl)-4-chlorocyclobutan-1-ones of the formula I in 2-(2<1>,2<1 ->dibromo-vinyl)-cyclopropanecarboxylic acid derivatives of formula VIII in aqueous-organic or organic medium are lower alcohols, e.g. those with 1 to 6 carbon atoms, benzyl alcohol, aliphatic or cyclic ethers, such as diethyl ether, di-n-propyl ether, di-isopropyl ether, tetrahydrofuran and dioxane, as well as aliphatic, cycloaliphatic or aromatic hydrocarbons, such as n-pentane, n-hexane, cyclohexane, benzene, toluene and xylenes.
Omsetningen av 2-(2<1>,2',2'-tribrometyl)-4-klorcyklobutan-l-oner med formelen I til 2-(2',21-dibromvinyl)-cyklopropankarbonsyre-derivater med formelen VIII foretas vanligvis ved det valgte reaksjonsmediets kokepunkt. Spesielt egnet er reaksjonstempera-turer mellom 40 og 120°C. The reaction of 2-(2<1>,2',2'-tribromomethyl)-4-chlorocyclobutan-1-ones of the formula I to 2-(2',21-dibromovinyl)-cyclopropanecarboxylic acid derivatives of the formula VIII is usually carried out by the boiling point of the selected reaction medium. Particularly suitable are reaction temperatures between 40 and 120°C.
Ved overføringen av 2-(2',2',2'-tribrometyl)-4-klorcyklobutan-l-oner med formelen I til 2-(2<1>,2'-dibromvinyl)-cyklopropankar-bonsyrederivater med formelen VIII opptrer intermediært de tilsvarende 2-(2',2<1>,2<1->tribrometyl)-cyklopro<p>ankarbonsyrederiva-ter med formelen X In the transfer of 2-(2',2',2'-tribromomethyl)-4-chlorocyclobutan-1-ones of the formula I to 2-(2<1>,2'-dibromovinyl)-cyclopropanecarboxylic acid derivatives of the formula VIII occurs intermediately the corresponding 2-(2',2<1>,2<1->tribromethyl)-cyclopropanecarboxylic acid derivatives with the formula X
hvor R, R-^, R2og X har de angitte betydninger, som mellomprodukter. Disse produkter kan oppfanges når man holder reaksjons-temperaturen under 40°C og/eller anvender et underskudd av base. Disse mellomprodukter går over 40°C ved tilsetning av ytterligere base under HX-avspaltning over i de tilsvarende 2-(2',2'-dibromvinyl)-cyklopropankarbonsyrederivater med formelen VIII. where R, R-^, R 2 and X have the indicated meanings, as intermediates. These products can be collected when keeping the reaction temperature below 40°C and/or using a deficit of base. These intermediates pass above 40°C upon addition of further base during HX cleavage into the corresponding 2-(2',2'-dibromovinyl)-cyclopropanecarboxylic acid derivatives of the formula VIII.
2-(2 *,21,2'-tribrometyl)-cyklopropankarbonsyrederivatene med formelen X kan også fremstilles ved bestråling med UV-lys, eventuelt under tilsetning av vanlige sensibilisatorer (f.eks. ketoner, som aceton, cykloheksanon, benzofenon, acetofenon og høy-ere alkylarylketoner, tioxanton, etc.) i nærvær av hydroksylgruppeholdige reagenser, som samtidig kan tjene som løsnings-middel, fotokjemisk ut fra 2-(2<1>,2',2<1>,-tribrometyl)-4-klor-cyklbbutan-l-oner med formelen I. Hydroksylgruppeholdige reagenser er f.eks. alkanoler, som metanol, etanol etc. og frem for alt vann. The 2-(2*,21,2'-tribromethyl)-cyclopropanecarboxylic acid derivatives of the formula X can also be prepared by irradiation with UV light, optionally with the addition of common sensitizers (e.g. ketones, such as acetone, cyclohexanone, benzophenone, acetophenone and higher alkylaryl ketones, thioxanthone, etc.) in the presence of reagents containing hydroxyl groups, which can simultaneously serve as solvents, photochemically from 2-(2<1>,2',2<1>,-tribromethyl)-4- chloro-cyclobbutan-1-ones with the formula I. Reagents containing hydroxyl groups are e.g. alkanols, such as methanol, ethanol etc. and above all water.
Fremgangsmåten ifølge oppfinnelsen anskueliggjøres nærmere ved^de følgende eksempler.. The method according to the invention is illustrated in more detail by the following examples.
l l
I EKSEMPEL IN EXAMPLE
a) , Fremstilling av 4, 4, 4- tribromsmørsyreklorid 324,3 g (1,0 mol) 4,4,4-tribromsmørsyre oppvarmes med 600 g a), Preparation of 4, 4, 4-tribromobutyric acid chloride 324.3 g (1.0 mol) 4,4,4-tribromobutyric acid is heated with 600 g
tionylklorid og 1 ml dimetylformamid først i 2 timer ved 40°C og deretter i 3 timer ved 75°C. Deretter avdestilleres det overskytende tionylklorid og resten rektifiseres i høyvakuum. Man får 326,0 g (95% av teoretisk utbytte) 4,4,4-tribromsmør-syreklorid med kokepunkt 71 til 73°C / 0,05 Torr. thionyl chloride and 1 ml of dimethylformamide first for 2 hours at 40°C and then for 3 hours at 75°C. The excess thionyl chloride is then distilled off and the residue is rectified in a high vacuum. 326.0 g (95% of theoretical yield) of 4,4,4-tribromobutyric acid chloride with boiling point 71 to 73°C / 0.05 Torr is obtained.
b) Fremstilling av 2- klor- 4, 4, 4- tribromsmørsyreklorid 343,2 g (1,0 mol) 4,4,4-tribromsmørsyreklorid løses i 600 g b) Preparation of 2-chloro-4,4,4-tribromobutyric acid chloride Dissolve 343.2 g (1.0 mol) of 4,4,4-tribromobutyric acid chloride in 600 g
tionylklorid og blandes ved 60°C under samtidig belysning med en kvikksølv-høytrykkslampe porsjonsvis med 266,0 g (2,0 mol) N-klorsuccinimid. Etter avsluttet tilsetning av N-klorsuccini-midet røres den erholdte blanding 5 timer ved 60°C under belysning. Derpå avdestilleres tionylkloridet og resten rektifiseres i høyvakuum. Man får 309,7 g (82% av det teoretiske) 2-klor-4,4,4-tribromsmørsyreklorid med kokepunkt 59 til 63°C/ 0,05 Torr. thionyl chloride and mixed at 60°C under simultaneous illumination with a mercury high-pressure lamp in portions with 266.0 g (2.0 mol) of N-chlorosuccinimide. After completion of the addition of the N-chlorosuccinimid, the resulting mixture is stirred for 5 hours at 60°C under illumination. The thionyl chloride is then distilled off and the residue is rectified under high vacuum. 309.7 g (82% of the theoretical) of 2-chloro-4,4,4-tribromobutyric acid chloride with a boiling point of 59 to 63°C/ 0.05 Torr are obtained.
c) Fremstilling av 2-( 2', 2', 2'- tribrometyl)- 2- klor- 3, 3- di-me ty1cyk1obut an- 1-o n c) Preparation of 2-(2', 2', 2'-tribromethyl)-2-chloro-3,3-di-methy1cyclobutan-1-one
I en autoklav anbringes 90,6 g (0,24 mol) 2-klor-4,4,4-tri-bromsmørsyreklorid i 360 ml cykloheksan og 134 g (2,4 mol) isobutylen presses inn. Deretter tilpumpes ved 65°C i 4 timer en løsning av 24,2 g (0,24 mol) trietylamin i 120 ml cykloheksan. Etter avsluttet tilsetning av trietylaminløsningen holdes reaksjonsblandingen ytterligere 3 timer ved 65°C. Derpå frafiltre-res det dannete trietylaminohydroklorid og løsningsmidlet avdestilleres. Resten løses i en løsningsmiddelblanding bestående av like deler toluen og heksan og filtreres på kiselgel. Etter avdampning av løsningsmidlet får man ut av filtratet 51,4 g (54 % av det teoretiske utbytte) 2-(2',2',21-tribrometyl)-2-klor-3,3-dimetylcyklobutan-l-on med smeltepunkt 95 til 97°C. IR-spektrum (CC14) i cm"<1>: 1800 (CO). In an autoclave, 90.6 g (0.24 mol) of 2-chloro-4,4,4-tribromobutyric acid chloride are placed in 360 ml of cyclohexane and 134 g (2.4 mol) of isobutylene is pressed in. A solution of 24.2 g (0.24 mol) of triethylamine in 120 ml of cyclohexane is then pumped in at 65°C for 4 hours. After the addition of the triethylamine solution is finished, the reaction mixture is kept for a further 3 hours at 65°C. The formed triethylaminohydrochloride is then filtered off and the solvent is distilled off. The residue is dissolved in a solvent mixture consisting of equal parts toluene and hexane and filtered on silica gel. After evaporation of the solvent, 51.4 g (54% of the theoretical yield) of 2-(2',2',21-tribromomethyl)-2-chloro-3,3-dimethylcyclobutan-1-one with melting point 95 to 97°C. IR spectrum (CC14) in cm"<1>: 1800 (CO).
■'■H-NMR-spektrum (100 MHz, CDC13) i ppm: 1,39 og 1,41 (ls; ■'■H-NMR spectrum (100 MHz, CDCl 3 ) in ppm: 1.39 and 1.41 (ls;
3H) ; 2,86-3,22 (m; 2H) 3,55-4,15 (m, 2H) . 3H); 2.86-3.22 (m; 2H) 3.55-4.15 (m, 2H).
i ' d) Fremstilling av 2- ( 2 ' , 2 ', 2 '- tribrometyl)- 3 , 3- dimetyl- 4- i 'd) Preparation of 2-(2',2',2'-tribromethyl)-3,3-dimethyl-4-
klorcykTobutan- l- on chlorocycloTobutan- l- one
I 220 ml absolutt etanol løses etter metning med hydrogenklorid 22,8 g (0,054 mol) 2-(2•,2',2<1->tribrometyl)-2-klor-3,3-di-metylcyklobutan-l-on. Den erholdte løsning røres 5 timer ved 80°C. Derpå konsentreres reaksjonsblandingen på rotasjonsfor-damper til ca. 1/3 av det opprinnelige volum, blandes med vann og ekstraheres med eter. E^erekstraktet vaskes først med mettet koksaltlsøning, deretter med natriumbikarbonatløsning og tørkes over natriumsulfat. Resten som erholdes etter avdampningen av eteren kromatograferes på kiselgel, hvorved toluen tjener som elueringsmiddel. Etter forening og inndampning av. de rene frak-sjonene får man 17,1 g (75 % av det teoretiske utbytte) 2-(2<1>,2<1>,2<1->tribrometyl)-3,3-dimetyl-4-klorcyklobutan-l-on med After saturation with hydrogen chloride, 22.8 g (0.054 mol) of 2-(2•,2',2<1->tribromethyl)-2-chloro-3,3-dimethylcyclobutan-1-one are dissolved in 220 ml of absolute ethanol . The resulting solution is stirred for 5 hours at 80°C. The reaction mixture is then concentrated on a rotary evaporator to approx. 1/3 of the original volume, mixed with water and extracted with ether. The egg extract is first washed with saturated sodium bicarbonate solution, then with sodium bicarbonate solution and dried over sodium sulfate. The residue obtained after evaporation of the ether is chromatographed on silica gel, whereby toluene serves as eluent. After union and evaporation of. the pure fractions yield 17.1 g (75% of the theoretical yield) 2-(2<1>,2<1>,2<1->tribromethyl)-3,3-dimethyl-4-chlorocyclobutane- l-on with
smeltepunkt 87-89°C. melting point 87-89°C.
IR-spektrum (CC1,) i cm"<1>: 1805 (CO), IR spectrum (CC1,) in cm"<1>: 1805 (CO),
i H-NMR-spektrum 4(100 MHz, (CDC13) i ppm: 1,14 og 1,67 (1 s; 3H); in H-NMR spectrum 4 (100 MHz, (CDCl 3 ) in ppm: 1.14 and 1.67 (1 s; 3H);
3,08 til 3,68 (m; 3H); 4,77 (d; 1H).-e) Fremstilling av 2-( 2', 2'- dibromvinyl)- 3, 3- dimetylcyklo-propan- l- karbonsyre 3.08 to 3.68 (m; 3H); 4.77 (d; 1H).-e) Preparation of 2-(2',2'-dibromovinyl)-3,3-dimethylcyclopropane-1-carboxylic acid
800 g (2 mmol) 2-(2',2<1>,2<1->tribrometyl)-3,3-dimetyl-4-klorcyklo-butan-l-on tilsettes ved 0°C 5,6 ml 5%'ig natronlut. Den erholdte blanding røres først 18 timer ved 0°C og deretter 1 time ved 80°C. Derpå vaskes reaksjonsblandingen først med dietyleter og surgjøres så under kjøling med konsentrert saltsyre og ekstraheres med dietyleter. Ekstraktet vaskes med vann, tørkes 800 g (2 mmol) 2-(2',2<1>,2<1->tribromethyl)-3,3-dimethyl-4-chlorocyclo-butan-1-one are added at 0°C 5.6 ml 5 % caustic soda. The resulting mixture is first stirred for 18 hours at 0°C and then for 1 hour at 80°C. The reaction mixture is then first washed with diethyl ether and then acidified under cooling with concentrated hydrochloric acid and extracted with diethyl ether. The extract is washed with water, dried
over magnesiumsulfat og inndampes. Man får 0,59 g (100% av det teoretiske utbytte) 2-(2',2<1->dibromvinyl)-3,3-dimetylcyklopropan-1-karbonsyre, som består av 80 vekts% cis-isomer og 20 vekts% trans-isomer. over magnesium sulfate and evaporate. 0.59 g (100% of the theoretical yield) of 2-(2',2<1->dibromovinyl)-3,3-dimethylcyclopropane-1-carboxylic acid is obtained, which consists of 80% by weight of the cis-isomer and 20% by weight % trans isomer.
IR-spektrum (CHC13) i cm"<1>: 1695 (CO). IR spectrum (CHCl 3 ) in cm"<1>: 1695 (CO).
<1>H-NMR-spektrum (100 MHz, CDCI3) i ppm: 1,25 og 1,35, samt 1,30 og i,31 (1 s; 2 CH-^-grupper av trans- og cis-forbindelsen); <1>H-NMR spectrum (100 MHz, CDCl3) in ppm: 1.25 and 1.35, as well as 1.30 and i.31 (1 s; 2 CH-^ groups of the trans and cis compound );
1,62 til 2,30 (m; 2H), 6,15 og 6,70 (1 d; intensitetsforhold 1:4, totalt integral 1H). 1.62 to 2.30 (m; 2H), 6.15 and 6.70 (1 d; intensity ratio 1:4, total integral 1H).
Claims (1)
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NO783313A NO783313L (en) | 1978-09-29 | 1978-09-29 | PROCEDURE FOR THE PREPARATION OF 2- (2`, 2`, 2`-TRIBROMETHYL) -4-CHLORICYCLOBUTAN-1-ONER |
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NO783313A NO783313L (en) | 1978-09-29 | 1978-09-29 | PROCEDURE FOR THE PREPARATION OF 2- (2`, 2`, 2`-TRIBROMETHYL) -4-CHLORICYCLOBUTAN-1-ONER |
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