IT8322161A1 - PROCESS FOR THE PREPARATION OF CHLORIDES, BROMIDES OR IODIDE OF AROMATIC CARBOXYLIC ACIDS - Google Patents
PROCESS FOR THE PREPARATION OF CHLORIDES, BROMIDES OR IODIDE OF AROMATIC CARBOXYLIC ACIDS Download PDFInfo
- Publication number
- IT8322161A1 IT8322161A1 IT1983A22161A IT2216183A IT8322161A1 IT 8322161 A1 IT8322161 A1 IT 8322161A1 IT 1983A22161 A IT1983A22161 A IT 1983A22161A IT 2216183 A IT2216183 A IT 2216183A IT 8322161 A1 IT8322161 A1 IT 8322161A1
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- IT
- Italy
- Prior art keywords
- palladium
- chloride
- iodide
- bromide
- alkaline
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims description 22
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 title claims description 20
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 title claims description 16
- 238000002360 preparation method Methods 0.000 title claims description 7
- 150000001735 carboxylic acids Chemical class 0.000 title description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 45
- 229910052763 palladium Inorganic materials 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- -1 aromatic carboxylic acids Chemical class 0.000 claims description 18
- 150000001491 aromatic compounds Chemical class 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000001805 chlorine compounds Chemical class 0.000 claims description 7
- 150000001649 bromium compounds Chemical class 0.000 claims description 6
- 150000004694 iodide salts Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Inorganic materials [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 13
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 12
- 229940095102 methyl benzoate Drugs 0.000 description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 7
- 101150003085 Pdcl gene Proteins 0.000 description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 150000002940 palladium Chemical class 0.000 description 4
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 238000006280 Rosenmund reaction Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- YJMNOKOLADGBKA-UHFFFAOYSA-N cyanonaphthalene Natural products C1=CC=C2C(C#N)=CC=CC2=C1 YJMNOKOLADGBKA-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-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
- 239000011780 sodium chloride Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical class C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 1
- GVEDOIATHPCYGS-UHFFFAOYSA-N 1-methyl-3-(3-methylphenyl)benzene Chemical group CC1=CC=CC(C=2C=C(C)C=CC=2)=C1 GVEDOIATHPCYGS-UHFFFAOYSA-N 0.000 description 1
- NPDIDUXTRAITDE-UHFFFAOYSA-N 1-methyl-3-phenylbenzene Chemical group CC1=CC=CC(C=2C=CC=CC=2)=C1 NPDIDUXTRAITDE-UHFFFAOYSA-N 0.000 description 1
- IDTDAMGQDWDZEU-UHFFFAOYSA-N 1-methylnaphthalene-2-carboxylic acid Chemical class C1=CC=C2C(C)=C(C(O)=O)C=CC2=C1 IDTDAMGQDWDZEU-UHFFFAOYSA-N 0.000 description 1
- NWPNXBQSRGKSJB-UHFFFAOYSA-N 2-methylbenzonitrile Chemical compound CC1=CC=CC=C1C#N NWPNXBQSRGKSJB-UHFFFAOYSA-N 0.000 description 1
- ZSPDYGICHBLYSD-UHFFFAOYSA-N 2-methylnaphthalene-1-carboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C)=CC=C21 ZSPDYGICHBLYSD-UHFFFAOYSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical group C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- RJTJVVYSTUQWNI-UHFFFAOYSA-N beta-ethyl naphthalene Natural products C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 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
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- XCTLDQQOHIEUCJ-UHFFFAOYSA-N ethyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OCC)=CC=CC2=C1 XCTLDQQOHIEUCJ-UHFFFAOYSA-N 0.000 description 1
- HQKSINSCHCDMLS-UHFFFAOYSA-N ethyl naphthalene-2-carboxylate Chemical compound C1=CC=CC2=CC(C(=O)OCC)=CC=C21 HQKSINSCHCDMLS-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000005350 hydroxycycloalkyl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 206010022000 influenza Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- IODOXLXFXNATGI-UHFFFAOYSA-N methyl naphthalene-2-carboxylate Chemical compound C1=CC=CC2=CC(C(=O)OC)=CC=C21 IODOXLXFXNATGI-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical class [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PEQHIRFAKIASBK-UHFFFAOYSA-N tetraphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 PEQHIRFAKIASBK-UHFFFAOYSA-N 0.000 description 1
- 150000005199 trimethylbenzenes Chemical class 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Descrizione dell'invenzione industriale dal titolo: "PROCESSO PER LA PREPARAZIONE DI CLORURI, BROMURI 0 IODURI DI ACIDI CARBOSSILICI AROMATICI" Description of the industrial invention entitled: "PROCESS FOR THE PREPARATION OF CHLORIDES, BROMIDES OR IODIDE OF AROMATIC CARBOXYLIC ACIDS"
Riassunto Summary
L'invenzione riguarda un processo per la preparazione di cloruri, bromuri o ioduri di acidi carbossilici aromatici, in cui un composto aromatico contenente almeno un atomo di idrogeno legato ad un atomo di carbonio di un nucleo aromatico viene fatto reagire con ossido di carbonio e cloruro, bromuro o ioduro rameico a temperature comprese fra 0 e 300?C e sotto una pressione di ossido di carbonio compresa fra 1 e 300 atmosfere. Il processo ? caratterizzato dal fatto che la reazione viene effettuata in un solvente clorurato e in presenza: 1?) di palladio, un sale di palladio bivalente o un complesso di palladio zerovalente e 2?) di un cloruro, bromuro o ioduro alcalino . The invention relates to a process for the preparation of chlorides, bromides or iodides of aromatic carboxylic acids, in which an aromatic compound containing at least one hydrogen atom bonded to a carbon atom of an aromatic nucleus is reacted with carbon monoxide and chloride , bromide or cupric iodide at temperatures between 0 and 300 ° C and under a carbon monoxide pressure between 1 and 300 atmospheres. The process ? characterized in that the reaction is carried out in a chlorinated solvent and in the presence: 1) of palladium, a salt of divalent palladium or a complex of zerovalent palladium and 2) of a chloride, bromide or alkaline iodide.
La presente invenzione riguarda un procedimento per la preparazione di cloruri, bromuri o ioduri di acidi carbossilici aromatici . Questi alogenuri di acile possono essere convertiti facilmente in acidi ed esteri carbossilici aromatici. Possono pure essere convertiti nelle corrispondenti aldeidi mediante la reazione di Rosenmund. The present invention relates to a process for the preparation of chlorides, bromides or iodides of aromatic carboxylic acids. These acyl halides can be easily converted to aromatic carboxylic acids and esters. They can also be converted into the corresponding aldehydes by the Rosenmund reaction.
Questi acidi, esteri ed aldeidi trovano svariati impieghi. Ad esempio l'acido benzoico ? un utile intermedio per varie sintesi mentre i suoi esteri sono largamente impiegati come plastificanti, mentre la benzaldeide ? un noto intermedio, in particolare per la preparazione di coloranti. These acids, esters and aldehydes find various uses. For example benzoic acid? a useful intermediate for various syntheses while its esters are widely used as plasticizers, while benzaldehyde? a known intermediate, in particular for the preparation of dyes.
E ' noto preparare cloruri di acidi carbossilici aromatici per reazione di un composto aromatico contenente almeno un atomo di idrogeno legato ad un atomo di carbonio di un nucleo aromatico con ossido di carbonio e PdCl , eventualmente in presenza di CuCl2* Le rese di questo processo sono basse. It is known to prepare chlorides of aromatic carboxylic acids by reaction of an aromatic compound containing at least one hydrogen atom bonded to a carbon atom of an aromatic nucleus with carbon monoxide and PdCl, possibly in the presence of CuCl2 * The yields of this process are low.
Uno scopo della presente invenzione ? quello di fornire un processo per preparare cloruri, bromuri o ioduri di acidi carbossilici aromatici per reazione di un siffatto composto aromatico con ossido di carbonio, ottenendo buone rese. A purpose of the present invention? that of providing a process for preparing chlorides, bromides or iodides of aromatic carboxylic acids by reaction of such an aromatic compound with carbon monoxide, obtaining good yields.
Un altro scopo della presente invenzione ? quello di fornire un processo che dia una buona selettivit? nel prodotto desiderato . Another object of the present invention? to provide a process that gives good selectivity? in the desired product.
Questi scopi ed altri ancora vengono raggiunti dal processo oggetto della presente invenzione, per la preparazione di cloruri, bromuri o ioduri di acidi carbossilici aromatici, in cui un composto aromatico contenente almeno un atomo di idrogeno legato ad un atomo di carbonio di un nucleo aromatico viene fatto reagire con ossido di carbonio e cloruro, bromuro o ioduro rameico a temperature comprese fra 0 e 300?C e sotto una pressione di ossido di carbonio compresa fra 1 e 300 atmosfere. Il processo ? caratterizzato dal fatto che la reazione viene effettuata in un solvente clorurato e in presenza: 1?) di palladio, un sale di palladio bivalente o un complesso di palladio zerovalente e 2?) di un cloruro, bromuro o ioduro alcalino . These objects and others besides are achieved by the process object of the present invention, for the preparation of chlorides, bromides or iodides of aromatic carboxylic acids, in which an aromatic compound containing at least one hydrogen atom bonded to a carbon atom of an aromatic nucleus is reacted with carbon monoxide and chloride, bromide or cupric iodide at temperatures between 0 and 300 ° C and under a carbon monoxide pressure between 1 and 300 atmospheres. The process ? characterized in that the reaction is carried out in a chlorinated solvent and in the presence: 1) of palladium, a salt of divalent palladium or a complex of zerovalent palladium and 2) of a chloride, bromide or alkaline iodide.
Si ? difatti trovato, in conformit? alla presente invenzione, che la resa della reazione aumenta notevolmente quando si opera in un solvente clorurato e in presenza di un cloruro, bromuro o ioduro alcalino. Inoltre, oltre ai sali di palladio si possono usare, secondo la presente invenzione, palladio metallico e complessi di palladio zerovalente. Yup ? in fact found, in conformity? to the present invention, that the reaction yield increases considerably when operating in a chlorinated solvent and in the presence of an alkaline chloride, bromide or iodide. Furthermore, in addition to the palladium salts, metallic palladium and zerovalent palladium complexes can be used according to the present invention.
La reazione della presente invenzione ? rappresentata dalla seguente equazione, in cui Ar-H indica un composto aromatico e X indica Cl, Br o I. The reaction of the present invention? represented by the following equation, where Ar-H indicates an aromatic compound and X indicates Cl, Br or I.
(1) (1)
Il palladio metallico pu? essere utilizzato tale e quale o fissato su vari supporti, come ad esempio la silice, il carbone attivo e il solfato di bario. Il sale di palladio ? costituito da un qualsiasi sale del palladio (II) di un acido minerale o organico, quali per esempio il nitrato, il solfato, il cloruro, il bromuro, il fluoruro, lo ioduro, l'acetato l 'acetilacetonato o il trifluoracetato. Preferibilmente si usa, come sale di palladio, PdCl9. I complessi di palladio zerovalente sono ad esempio quelli con fosfine (ad esempio Pd P(fenile) e quello con dibenzilidenacetone . Metallic palladium can? be used as it is or fixed on various supports, such as silica, activated carbon and barium sulphate. The palladium salt? consisting of any palladium (II) salt of a mineral or organic acid, such as for example nitrate, sulphate, chloride, bromide, fluoride, iodide, acetate, acetylacetonate or trifluoracetate. Preferably, PdCl9 is used as the palladium salt. The zerovalent palladium complexes are for example those with phosphines (for example Pd P (phenyl) and the one with dibenzylidene acetone.
Come sale rameico si usa preferibilmente il cloruro, producendo in conseguenza il cloruro dell'acido carbossilico . Chloride is preferably used as the cupric salt, consequently producing the chloride of the carboxylic acid.
Il solvente clorurato ? preferibilmente un solvente clorurato polare, in particolare il cloroformio. The chlorinated solvent? preferably a polar chlorinated solvent, in particular chloroform.
Il cloruro, bromuro o ioduro alcalino ? preferibilmente il cloruro, bromuro o ioduro di litio o sodio. Is chloride, bromide or alkaline iodide? preferably lithium or sodium chloride, bromide or iodide.
Il composto aromatico di partenza pu? essere monociclico, policiclico non condensato o policiclico ad anelli condensati. Esso contiene comunemente da uno a cinque nuclei benzenici. Pu? contenere dei gruppi sostituenti, inerti nelle condizioni di reazione, sui nuclei aromatici. Comunemente sono presenti da 0 a 5 gruppi sostituenti. Tali gruppi, uguali o diversi fra di loro, sono in particolare: The starting aromatic compound can? be monocyclic, non-condensed polycyclic or polycyclic with condensed rings. It commonly contains one to five benzene nuclei. Pu? contain substituent groups, inert under the reaction conditions, on the aromatic nuclei. Commonly there are 0 to 5 substituent groups. These groups, the same or different from each other, are in particular:
1?) i gruppi alchilici o i residui di idrocarburi aliciclici. 1?) Alkyl groups or alicyclic hydrocarbon residues.
I gruppi alchilici contengono comunemente da 1 a 4 atomi di carbonio e sono ad esempio i gruppi metile, etile, n. propile e isopropile. I residui di idrocarburi aliciclici contengono comunemente da 1 a 10 atomi di carbonio e sono, ad esempio, i gruppi cicloesile, metilcicloesile , dimet ilcicloesile , etilcicloesile e propilcicloesile . The alkyl groups commonly contain from 1 to 4 carbon atoms and are for example the methyl, ethyl, n groups. propyl and isopropyl. The residues of alicyclic hydrocarbons commonly contain from 1 to 10 carbon atoms and are, for example, the cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl and propylcyclohexyl groups.
2?) i gruppi idrossialchilici o idrossicicloalchilici . Trattasi di gruppi alchilici o residui di idrocarburi aliciclici come descritti in 1?) aventi un sostituente idrossi. Questi gruppi sono, ad esempio, l'idrossimet ile e l'idrossietile. 2?) The hydroxyalkyl or hydroxycycloalkyl groups. These are alkyl groups or residues of alicyclic hydrocarbons as described in 1?) Having a hydroxy substituent. These groups are, for example, hydroxymethyl and hydroxyethyl.
3?) i gruppi alcossi derivati dai gruppi alchilici descritti in 1?), ad esempio i gruppi metossi ed etossi. 3?) The alkoxy groups derived from the alkyl groups described in 1?), For example the methoxy and ethoxy groups.
4?) il gruppo carbossilico . 4?) The carboxyl group.
5? ) i gruppi esteri in cui i gruppi alchilici o i residui di idrocarburi aliciclici descritti in 1?) esterificano gruppi carbossilici legati ad un nucleo aromatico. Tali gruppi esteri sono ad esempio -COOCH , -COOC H , -COOC H e -COOC H . 5? ) ester groups in which the alkyl groups or residues of alicyclic hydrocarbons described in 1?) esterify carboxylic groups bonded to an aromatic nucleus. Such ester groups are for example -COOCH, -COOC H, -COOC H and -COOC H.
6?) il gruppo ciano. 6?) The cyan group.
7?) il gruppo nitro. 7?) The nitro group.
8?) gli alogeni, in particolare il fluoro e il cloro. 8?) Halogens, in particular fluorine and chlorine.
9? ) i gruppi acile R-CO in cui R ? un residuo idrocarburico avente da 1 a 10 atomi di carbonio, per esempio i gruppi acetile, propionile e benzoile. 9? ) the acyl groups R-CO in which R? a hydrocarbon residue having from 1 to 10 carbon atoms, for example the acetyl, propionyl and benzoyl groups.
I suddetti gruppi sostituenti possono anche trovarsi su una catena alchilica o un ciclo alifatico presenti nella sostanza aromatica. The above substituent groups can also be found on an alkyl chain or an aliphatic cycle present in the aromatic substance.
Fra gli idrocarburi aromatici che possono essere impiegati come sostanze di partenza nel processo della presente invenzione, si possono citare: il benzene, il toluene, lo xilene (o, m, ?), l'etilbenzene, il eumene, i trimetilbenzeni, il tetrametiIbenzene, il naftalene, l'alfametilnaftalene, il betametilnaftalene, i dimetilnaftaleni, l'etilnaftalene, 1'antracene, il fenantrene, il difenile, il 4-metil-difenile, il 3-metildifenile, il 3,3'-dimetildifenile, il trifenilmetano e il tetrafenilmetano. Among the aromatic hydrocarbons that can be used as starting substances in the process of the present invention, we can mention: benzene, toluene, xylene (o, m,?), Ethylbenzene, cumene, trimethylbenzenes, tetramethylbenzene , naphthalene, alpha amethylnaphthalene, betamethylnaphthalene, dimethylnaphthalenes, ethylnaphthalene, anthracene, phenanthrene, diphenyl, 4-methyl-diphenyl, 3-methyldiphenyl, 3,3'-dimethyldiphenyl, triphenylmethane and tetraphenylmethane.
Fra gli acidi carbossilici e loro esteri che possono essere impiegati come sostanze di partenza, si possono citare ad esempio: .l'acido benzoico, il metilbenzoato, 1'etilbenzoato, l'acido toluico (o, m, p), l'estere metilico dell'acido toluico (o, m, p), l'acido alfa-naftoico, l'acido beta-naftoico, gli acidi metil-alfa-naftoici, gli acidi metil-beta-naftoici,il metilestere dell'acido alfa-naftoico, il metil estere dell'acido beta-naftoico, l'estere etilico dell'acido alfa-naftoico, l'estere etilico dell'acido beta-naftoico, l'acido difenilmonocarbossilico (2-, 3-j o 4-) e i suoi esteri metilico, etilico, propilico e butilico. Among the carboxylic acids and their esters which can be used as starting substances, we can mention for example: benzoic acid, methylbenzoate, ethylbenzoate, toluic acid (o, m, p), ester toluic acid methyl (o, m, p), alpha-naphthoic acid, beta-naphthoic acid, methyl-alpha-naphthoic acids, methyl-beta-naphthoic acids, alpha-methyl ester naphthoic acid, beta-naphthoic acid methyl ester, alpha-naphthoic acid ethyl ester, beta-naphthoic acid ethyl ester, diphenylmonocarboxylic acid (2-, 3-j or 4-) and its methyl, ethyl, propyl and butyl esters.
Fra gli eteri di partenza si possono citare, ad esempio, l'anisolo, il difeniletere, gli acidi carbossilici del difeniletere e gli esteri di questi ultimi. Among the starting ethers, for example, anisole, diphenylether, carboxylic acids of diphenylether and esters of the latter can be mentioned.
Altri composti aromatici di partenza sono, ad esempio, il monoclorobenzene, il diclorobenzene, il cloronaftalene, il benzonitrile, il toluonitrile, il cianonaftalene, il nitrobenzene e l'acetofenone. Other starting aromatic compounds are, for example, monochlorobenzene, dichlorobenzene, chloronaphthalene, benzonitrile, toluonitrile, cyanonaphthalene, nitrobenzene and acetophenone.
L'ossido di carbonio pu? essere usato da solo o in presenza di altri gas, quali l'idrogeno, che non influenzino la reazione. La pressione del CO o la sua pressione parziale nel miscuglio gassoso ? generalmente compresa fra 1 e 300 atmosfere e, preferibilmente, fra 2 e 100 atmosfere. Carbon monoxide can? be used alone or in the presence of other gases, such as hydrogen, which do not affect the reaction. The pressure of the CO or its partial pressure in the gaseous mixture? generally comprised between 1 and 300 atmospheres and, preferably, between 2 and 100 atmospheres.
La temperatura di reazione ? generalemnte compresa fra 0 e 300?C e, preferibilmente, fra 50 e 200?C. The reaction temperature? generally between 0 and 300 ° C and, preferably, between 50 and 200 ° C.
Il rapporto molare fra il palladio e il composto aromatico ? generalmente compreso fra 1:1 e 1:10.000 e preferibilmente fra 1:100 e 1:1000. The molar ratio of palladium to the aromatic compound? generally between 1: 1 and 1: 10,000 and preferably between 1: 100 and 1: 1000.
Il rapporto atomico Cu/Pd ? generalmente compreso fra 1:1 e 100:1 e preferibilmente fra 1:1 e 25:1? The atomic ratio Cu / Pd? generally between 1: 1 and 100: 1 and preferably between 1: 1 and 25: 1?
Il rapporto molare fra il CO e il composto aromatico assume valori diversi a seconda della natura del composto aromatico. Tale rapporto ? generalmente compreso fra 0,2:1 e 100:1 e preferibilmente fra 0,5:1 e 50:1? The molar ratio between CO and the aromatic compound assumes different values depending on the nature of the aromatic compound. Such a relationship? generally between 0.2: 1 and 100: 1 and preferably between 0.5: 1 and 50: 1?
Il cloruro, bromuro o ioduro alcalino ? generalmente presente in quantit? tale che il rapporto atomico metallo alcalino/palladio sia compreso fra 1:1 e 100:1 e preferibilmente fra 5:1 e 15:1. Is chloride, bromide or alkaline iodide? generally present in quantity? such that the alkali metal / palladium atomic ratio is between 1: 1 and 100: 1 and preferably between 5: 1 and 15: 1.
Il rapporto in volume composto aromatico/solvente ? generalmente compreso fra 1:1 e 1:100 e preferibilmente fra 1:2 e 1:8. The aromatic compound / solvent volume ratio? generally between 1: 1 and 1: 100 and preferably between 1: 2 and 1: 8.
Il tempo di reazione ? comunemente compreso fra 1 ora e 10 ore. The reaction time? commonly between 1 hour and 10 hours.
La separazione del prodotto di reazione pu? essere eseguita con tecniche convenzionali, ad esempio mediante distillazione The separation of the reaction product can? be performed with conventional techniques, for example by distillation
Il cloruro, il bromuro o l'ioduro di acido carbossilico possono essere facilmente trasformati nell'acido o nell'estere corrispondente per reazione con acqua o un alcool, secondo tecniche convenzionali . Possono anche essere trasformati in aldeide mediante la reazione di Rosenmund. The chloride, bromide or iodide of carboxylic acid can be easily transformed into the corresponding acid or ester by reaction with water or an alcohol, according to conventional techniques. They can also be transformed into aldehyde by the Rosenmund reaction.
Il cloruro, il bromuro o l'ioduro rameoso ottenuto alla fine della reazione pu? essere riossidato a cloruro, bromuro o ioduro rameico tramite la reazione seguente, in cui X rappresenta Cl, Br o I: The chloride, bromide or cuprous iodide obtained at the end of the reaction can? be reoxidized to chloride, bromide or cupric iodide by the following reaction, where X represents Cl, Br or I:
(2) (2)
In questa reazione si impiega acido cloridrico, bromidrico o iodidrico e si ossida Cu+ con l'ossigeno dell'aria. Questa reazione di riossidazione ? tenuta separata dalla reazione di carbonilazione evitando in tal modo la formazione di miscele esplosive di CO con 02 . In this reaction hydrochloric, hydrobromic or iodide acid is used and Cu + is oxidized with the oxygen in the air. This influenza reaction? kept separate from the carbonylation reaction thus avoiding the formation of explosive mixtures of CO with 02.
I seguenti esempi vengono forniti allo scopo di meglio illustrare il concetto inventivo del presente trovato. E' stato seguito il seguente modo generale di procedere: la miscela di reazione costituita dal composto aromatico, il solvente, il palladio o un suo sale bivalente o un suo complesso, l'alogenuro rameico e l'alogenuro alcalino viene preparata in un contenitore di vetro in ambiente di azoto. Il contenitore viene quindi introdotto in un'autoclave oscillante del volume di 250 cc. L'autoclave viene quindi chiusa, pressurizzata con CO, alla pressione desiderata, immersa in un bagno ad olio e scaldata alla temperatura voluta per il tempo stabilito. Al termine della prova si lascia raffreddare l 'autoclave a temperatura ambiente e si scarica la pressione residua di ossido di carbonio. La miscela di reazione viene trattata, a temperatura ambiente, con metanolo e Na2 CO3 per trasformare l'alogenuro di acido carbossilico nel corrispondente estere metilico. La miscela viene quindi filtrata. Il liquido raccolto viene analizzato quantitativamente tramite gas-cromatografia con standard interno. L'identificazione dei picchi ? effettuata mediante spettroscopia di massa organica o mediante risonanza magnetica nucleare. The following examples are provided in order to better illustrate the inventive concept of the present invention. The following general procedure was followed: the reaction mixture consisting of the aromatic compound, the solvent, palladium or a divalent salt thereof or a complex thereof, the cupric halide and the alkaline halide is prepared in a container of glass in a nitrogen environment. The container is then introduced into an oscillating autoclave with a volume of 250 cc. The autoclave is then closed, pressurized with CO, at the desired pressure, immersed in an oil bath and heated to the desired temperature for the set time. At the end of the test the autoclave is allowed to cool to room temperature and the residual carbon monoxide pressure is discharged. The reaction mixture is treated, at room temperature, with methanol and Na2 CO3 to transform the carboxylic acid halide into the corresponding methyl ester. The mixture is then filtered. The collected liquid is quantitatively analyzed by gas chromatography with internal standard. The identification of the peaks? performed by organic mass spectroscopy or by nuclear magnetic resonance.
Gli esempi 1, 2 e 3 sono esempi di confronto, in cui si impiega solo una parte dei componenti della presente invenzione. Vanno confrontati con l'esempio 4 dove, a parit? di condizioni, tutti i componenti vengono utilizzati. Examples 1, 2 and 3 are comparative examples, in which only a part of the components of the present invention are used. They should be compared with example 4 where, on a par? of conditions, all components are used.
ESEMPIO 1 EXAMPLE 1
Si mettono nell'autoclave 1 g di PdCl (5,6 mM, dove mM significa millimole), 12 g di CuCl ( 89 mM) e 80 cc di benzene, operando quindi in assenza di solvente e di alogenuro alcalino. L'autoclave viene chiusa, pressurizzata con 50 atmosfere di CO e riscaldata a 200?C per 4 ore. Al termine, la miscela di reazione viene trattata con 5 g di Na2 CO3 dispersi in 30 cc di metanolo. La miscela viene tenuta sotto agitazione fino a quando non si nota pi? sviluppo di CO2 ? Si trovano 1,7 g (12,5 mM) di benzoato di metile, corrispondenti ad una resa, calcolata rispetto a CuCl2, di 28%. 1 g of PdCl (5.6 mM, where mM means millimole), 12 g of CuCl (89 mM) and 80 cc of benzene are put in the autoclave, thus operating in the absence of solvent and alkaline halide. The autoclave is closed, pressurized with 50 atmospheres of CO and heated to 200 ° C for 4 hours. At the end, the reaction mixture is treated with 5 g of Na2 CO3 dispersed in 30 cc of methanol. The mixture is kept under stirring until it is no longer noticeable. CO2 development? 1.7 g (12.5 mM) of methyl benzoate are found, corresponding to a yield, calculated with respect to CuCl2, of 28%.
ESEMPIO 2 EXAMPLE 2
Si mettono nell'autoclave 1 g di PdCl2 (5,6 mM), 12 g di CuCl (89 mM), 5 g di LiCl (119 mM) e 80 cc di benzene. Si opera quindi in assenza di solvente. Si procede poi come nell'esempio 1, trovando 2,8 g (20,6 mM) di benzoato di metile, corrispondenti ad una resa, calcolata rispetto a CuCl2, di 46% . 1 g of PdCl2 (5.6 mM), 12 g of CuCl (89 mM), 5 g of LiCl (119 mM) and 80 cc of benzene are placed in the autoclave. It is therefore operated in the absence of solvent. One then proceeds as in example 1, finding 2.8 g (20.6 mM) of methyl benzoate, corresponding to a yield, calculated with respect to CuCl2, of 46%.
ESEMPIO 3 EXAMPLE 3
Si mettono nell'autoclave 1 g di PdCl (5,6 mM), 12 g di CuC.l2 ( 89 mM ), 20 cc di benzene e 60 cc di cloroformio, operando quindi in assenza di alogenuro alcalino. Si procede poi come nell'esempio 1, trovando 4,0 g (29,4 mM) di benzoato di metile, corrispondenti ad una resa, calcolata rispetto a CuCl2 , di 66%. 1 g of PdCl (5.6 mM), 12 g of CuCl2 (89 mM), 20 cc of benzene and 60 cc of chloroform are placed in the autoclave, thus operating in the absence of alkaline halide. One then proceeds as in example 1, finding 4.0 g (29.4 mM) of methyl benzoate, corresponding to a yield, calculated with respect to CuCl2, of 66%.
ESEMPIO 4 EXAMPLE 4
Si mettono nell'autoclave 1 g di PdCl (5,6 mM), 12 g di CuCl2 ( 89 mM), 5 g di LiCl (119 mM), 20 cc di benzene e 60 cc di cloroformio. Si procede poi come nell'esempio 1, trovando 5,5 g (40,5 mM) di benzoato di metile, corrispondenti ad una resa, calcolata rispetto a CuCl , di 91%? 1 g of PdCl (5.6 mM), 12 g of CuCl2 (89 mM), 5 g of LiCl (119 mM), 20 cc of benzene and 60 cc of chloroform are placed in the autoclave. One then proceeds as in example 1, finding 5.5 g (40.5 mM) of methyl benzoate, corresponding to a yield, calculated with respect to CuCl, of 91%?
ESMPIO 5 EXAMPLE 5
Si mettono nell'autoclave 1 g di Pd CI (5,6 mM ), 12 g di CuCl2 (89 mM), 2,5 g di LiCl (59,5 mM ), 20 cc di benzene e 60 cc di cloroformio. 1 g of Pd Cl (5.6 mM), 12 g of CuCl2 (89 mM), 2.5 g of LiCl (59.5 mM), 20 cc of benzene and 60 cc of chloroform are placed in the autoclave.
Si procede poi come nell'esempio 1, trovando 6,1 g (44,5 mM ) di benzoato di metile, corrispondenti ad una resa, calcolata rispetto a CuCl2 , di 100$. One then proceeds as in example 1, finding 6.1 g (44.5 mM) of methyl benzoate, corresponding to a yield, calculated with respect to CuCl2, of 100%.
ESEMPIO 6 EXAMPLE 6
Si mettono nell'autoclave 1 g di PdCl (5,6 mM), 12 g di CuCl (89 mM), S g di NaCl (86 mM ), 20 cc di benzene e 60 cc di cloroformio. Si procede poi come nell'esempio 1, trovando 5,2 g (38,4 mM ) di benzoato di metile corrispondenti ad una resa, calcolata rispetto a CuCl2 , di 86$. 1 g of PdCl (5.6 mM), 12 g of CuCl (89 mM), S g of NaCl (86 mM), 20 cc of benzene and 60 cc of chloroform are placed in the autoclave. One then proceeds as in example 1, finding 5.2 g (38.4 mM) of methyl benzoate corresponding to a yield, calculated with respect to CuCl2, of 86%.
ESEMPIO 7 EXAMPLE 7
Si mettono nell'autoclave 1 g di PdCl^ (5,6 mM), 12 g di CuCl2 ( 89 mM), 2,5 g di LiCl (59,5<? >mM), 20 cc di toluene e 60 cc di cloroformio. Si procede poi come nell'esempio 1, trovando 0,9 g (6,0 mM) di 1 g of PdCl ^ (5.6 mM), 12 g of CuCl2 (89 mM), 2.5 g of LiCl (59.5 <?> MM), 20 cc of toluene and 60 cc of chloroform. We then proceed as in example 1, finding 0.9 g (6.0 mM) of
corrispondenti ad una resa, calcolata rispetto a CuCl , di corresponding to a yield, calculated with respect to CuCl, of
ESEMPIO 8 EXAMPLE 8
Si mettono nell'autoclave 1 g di PdCl (5,6 mM), 12 g di CuCl2 (89 mM), 2,5 g di LiCl (59,5 mM), 20 cc di p-xilene e 60 cc di cloroformio. Si procede come nell'esempio 1, trovando 1 , 0 g ( 6 , 1 mM ) di 1 g of PdCl (5.6 mM), 12 g of CuCl2 (89 mM), 2.5 g of LiCl (59.5 mM), 20 cc of p-xylene and 60 cc of chloroform are placed in the autoclave. We proceed as in example 1, finding 1.0 g (6.1 mM) of
corrispondenti ad una resa, calcolata rispetto a CuCl2 di 14$. corresponding to a yield, calculated with respect to CuCl2 of 14 $.
ESEMPIO 9 EXAMPLE 9
Si usa un catalizzatore al palladio supportato su BaSO4: il catalizzatore contiene il 10% in peso di Pd . A palladium catalyst supported on BaSO4 is used: the catalyst contains 10% by weight of Pd.
Si mettono nell'autoclave 5 6 (4,7 milligrammi-atomi di Pd) del suddetto catalizzatore, 12 g di CuCl (89 rnM), 56 di LiCl (59,5 mM), 20 cc di benzene e 60 cc di cloroformio. 5 6 (4.7 milligrams-atoms of Pd) of the above catalyst, 12 g of CuCl (89 rnM), 56 of LiCl (59.5 mM), 20 cc of benzene and 60 cc of chloroform are placed in the autoclave.
Si procede poi come nell'esempio 1, trovando 2,8 g (20,6 mM) di benzoato di metile corrispondenti ad una resa, calcolata rispetto a CuCl , di 46%. One then proceeds as in example 1, finding 2.8 g (20.6 mM) of methyl benzoate corresponding to a yield, calculated with respect to CuCl, of 46%.
Claims (15)
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| Application Number | Priority Date | Filing Date | Title |
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| IT22161/83A IT1163827B (en) | 1983-07-21 | 1983-07-21 | PROCESS FOR THE PREPARATION OF CHLORIDE, BROMIDE OR IODIDE OF AROMATIC CARBOXYLIC ACIDS |
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| IT22161/83A IT1163827B (en) | 1983-07-21 | 1983-07-21 | PROCESS FOR THE PREPARATION OF CHLORIDE, BROMIDE OR IODIDE OF AROMATIC CARBOXYLIC ACIDS |
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| IT8322161A0 IT8322161A0 (en) | 1983-07-21 |
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| IT1163827B IT1163827B (en) | 1987-04-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IT22161/83A IT1163827B (en) | 1983-07-21 | 1983-07-21 | PROCESS FOR THE PREPARATION OF CHLORIDE, BROMIDE OR IODIDE OF AROMATIC CARBOXYLIC ACIDS |
Country Status (1)
| Country | Link |
|---|---|
| IT (1) | IT1163827B (en) |
-
1983
- 1983-07-21 IT IT22161/83A patent/IT1163827B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| IT1163827B (en) | 1987-04-08 |
| IT8322161A0 (en) | 1983-07-21 |
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