CN1304393A - 烷基一、烯基一和炔基氯的制备工艺 - Google Patents
烷基一、烯基一和炔基氯的制备工艺 Download PDFInfo
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- CN1304393A CN1304393A CN99806950A CN99806950A CN1304393A CN 1304393 A CN1304393 A CN 1304393A CN 99806950 A CN99806950 A CN 99806950A CN 99806950 A CN99806950 A CN 99806950A CN 1304393 A CN1304393 A CN 1304393A
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- -1 alkenyl chloride Chemical compound 0.000 title claims abstract description 65
- 150000001348 alkyl chlorides Chemical class 0.000 title abstract description 5
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000004202 carbamide Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 15
- 235000013877 carbamide Nutrition 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 12
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000006662 (C2-C4) acyloxy group Chemical group 0.000 claims description 10
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000006711 (C2-C12) alkynyl group Chemical group 0.000 claims description 3
- SNDGLCYYBKJSOT-UHFFFAOYSA-N 1,1,3,3-tetrabutylurea Chemical compound CCCCN(CCCC)C(=O)N(CCCC)CCCC SNDGLCYYBKJSOT-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- MNOILHPDHOHILI-UHFFFAOYSA-N Tetramethylthiourea Chemical compound CN(C)C(=S)N(C)C MNOILHPDHOHILI-UHFFFAOYSA-N 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000004415 heterocyclylalkyl group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- MEKMPQZLPWXFTF-UHFFFAOYSA-N 1-methyl-3-phenylimidazolidine Chemical class C1N(C)CCN1C1=CC=CC=C1 MEKMPQZLPWXFTF-UHFFFAOYSA-N 0.000 claims description 2
- LVPJVXIFAQRIKY-UHFFFAOYSA-N 1-methyl-3-propylideneurea Chemical compound CCC=NC(=O)NC LVPJVXIFAQRIKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000005020 hydroxyalkenyl group Chemical group 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 125000005016 hydroxyalkynyl group Chemical group 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 2
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 239000012320 chlorinating reagent Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 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 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229940051250 hexylene glycol Drugs 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 125000006033 1,1-dimethyl-2-propenyl group Chemical group 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
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- 125000006036 1-ethyl-1-propenyl group Chemical group 0.000 description 1
- 125000006037 1-ethyl-2-propenyl group Chemical group 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000006021 1-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000006030 1-methyl-3-butenyl group Chemical group 0.000 description 1
- 125000004806 1-methylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- 125000006022 2-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000006031 2-methyl-3-butenyl group Chemical group 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- NKTDTMONXHODTI-UHFFFAOYSA-N 2-pentyne Chemical compound CCC#CC NKTDTMONXHODTI-UHFFFAOYSA-N 0.000 description 1
- 125000003890 2-phenylbutyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000006041 3-hexenyl group Chemical group 0.000 description 1
- 125000006032 3-methyl-3-butenyl group Chemical group 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006042 4-hexenyl group Chemical group 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 125000004649 C2-C8 alkynyl group Chemical group 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- JHEPBQHNVNUAFL-UHFFFAOYSA-N hex-1-en-1-ol Chemical compound CCCCC=CO JHEPBQHNVNUAFL-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JICGTNNQQNZRHZ-UHFFFAOYSA-N oct-1-yn-1-ol Chemical compound CCCCCCC#CO JICGTNNQQNZRHZ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical compound CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- OKQKDCXVLPGWPO-UHFFFAOYSA-N sulfanylidenephosphane Chemical compound S=P OKQKDCXVLPGWPO-UHFFFAOYSA-N 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 125000004568 thiomorpholinyl group Chemical group 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0249—Ureas (R2N-C(=O)-NR2)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B39/00—Halogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及通过在催化剂存在下与氯化剂反应由醇制备烷基氯、烯基氯和炔基氯的工艺,其中所用催化剂为结构式(Ⅰ):R1R2CX－NR3R4的脲化合物,和/或通式(Ⅱ)的脲化合物,和/或通式(III)的脲化合物。
Description
本发明涉及在脲化合物存在下通过醇与氯化剂反应制备烷基-、烯基和炔基氯的新工艺。烷基-、烯基-和炔基氯化物是已知的并适合作为有机合成的有用中间体。它们可通过已知工艺由醇和光气在催化剂存在下反应而得到。
这样，GB-A 2 182 039公开了一种通过在三芳基膦氧化物或三芳基膦硫化物催化剂存在下与光气反应由醇制备烷基氯的工艺。EP-A514 683提出了作为催化剂的脂族磷化合物。
EP-A-200403公开了在未取代脲存在下烷氧基化合物的卤化反应。
这些工艺的缺点是会得到含磷的蒸馏残余物，由于形成磷酸而难于处理掉。
本发明的目的是纠正上述的不足，并特别地提供一种制备烷基-、烯基-和炔基氯的工艺，使得用少量的催化剂就可制备并基本上避免了副产物的形成。
发明人已发现上述目的由这样一种工艺可达到，即通过在催化剂存在下与氯化剂反应由醇制备烷基-、烯基-和炔基氯，其中催化剂是结构式(Ⅰ)的脲化合物：
R1R2N-CX-NR3R4 (Ⅰ)其中基团R1、R2、R3和R4可相同或不同，相互独立地是未取代或被1-3个C1-C4烷氧基、C2-C4酰基、C2-C4酰氧基、苯氧基、C2-C8二烷氨基、卤素、硝基和/或氰基取代的C1-C20烷基，C2-C12烯基，C2-C12炔基或者未取代或被1-3个C1-C4烷基、C1-C4烷氧基、C2-C4酰基、C2-C4酰氧基、苯氧基、C2-C8二烷氨基、卤素、硝基和/或氰基取代的C3-C12环烷基，C4-C12烷基环烷基，C4-C12环烷基烷基，杂环烷基，C5-C20杂环烷基烷基，C6-C14芳基，C7-C20芳烷基或C7-C20烷芳基，或其中基团R1或R2中的一个与基团R3或R4中的一个共同是未取代的或被1-3个C1-C4烷基、C1-C4烷氧基、C2-C4酰基、C2-C4酰氧基、苯氧基、C2-C8二烷氨基、卤素、硝基和氰基取代的C2-C12亚烷基链，该链可被醚、硫醚、叔氨基、酮、内酯、N-烷基取代的内酰胺或砜基团所中断，和其中X是氧或硫原子，和/或是通式(Ⅱ)的脲化合物：其中X有上述的含义，R5、R6、R7和R8可相同或不同，相互独立地具有对R1-R4给出的含义，
和/或是通式(Ⅲ)的化合物：其中X、R5-R8具有上述的含义，Z1、Z2可相同或不同，是未取代的或被1-3个C1-C4烷基、C1-C4烷氧基、C2-C4酰基、C2-C4酰氧基、苯氧基、C2-C8二烷氨基、卤素、硝基和/或氰基取代的亚甲基，亚乙基或亚乙烯基。
化合物Ⅰ、Ⅱ和Ⅲ中的有机取代基R1-R8相互独立有下列含义：
C1-C20烷基，优选C1-C12烷基，特别优选C1-C8烷基诸如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、正己基、异己基、正庚基、异庚基、正辛基和异辛基，尤其是C1-C4烷基诸如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基；
C2-C12烯基，优选C2-C8烯基，诸如乙烯基、1-丙烯基、2-丙烯基、1-甲基乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基、1-戊烯基、2-戊烯基、3-戊烯基、4-戊烯基、1-甲基-1-丁烯基、2-甲基-1-丁烯基、3-甲基-1-丁烯基、1-甲基-2-丁烯基、2-甲基-2-丁烯基、3-甲基-2-丁烯基、1-甲基-3-丁烯基、2-甲基-3-丁烯基、3-甲基-3-丁烯基、1,1-二甲基-2-丙烯基、1,2-二甲基丙烯基、1-乙基-1-丙烯基、1-乙基-2-丙烯基，1-己烯基、2-己烯基、3-己烯基、4-己烯基、5-己烯基，特别优选乙烯基、2-丙烯基和1-丁烯基；
C2-C12炔基，优选C2-C8炔基，诸如乙炔基，1-丙炔基、2-丙炔基、1-丁炔基、3-丁炔基、1-甲基-2-丙炔基、1-戊炔基、2-戊炔基、3-戊炔基、1-甲基-2-丁炔基、1-甲基-3-丁炔基、2-甲基-3-丁炔基、3-甲基-1-丁炔基、1,1-二甲基-2-丙炔基、1-乙基-2-丙炔基、1-己炔基、2-己炔基、3-己炔基、4-己炔基、5-己炔基，特别优选乙炔基、1-丙炔基和1-丁炔基。
所述基团可以被C1-C4烷氧基、C2-C4酰基、C2-C4酰氧基、苯氧基、C2-C8二烷氨基、卤素、硝基和/或氰基取代。优选取代的烷基，特别优选被卤素或氰基取代的烷基，例如氰甲基、氯甲基。
R1-R8也可以为：
C3-C12环烷基，优选C5-C8环烷基，诸如环戊基、环己基、环庚基或环辛基，特别优选环戊或或环己基，
C4-C12烷基环烷基，优选C5-C10烷基环烷基，特别优选C5-C8烷基环烷基，
C4-C12环烷基烷基，优选C5-C10环烷基烷基，特别优选C5-C8环烷基烷基，
C5-C20烷基环烷基烷基，优选C6-C16烷基环烷基烷基，特别优选C7-C12烷基环烷基烷基，
杂环烷基，诸如环中有1或2个O、N和/或S原子的5或元环，可以是芳族的或非芳族的，例如2或3-呋喃基、2或3-噻吩基、2或3-吡咯基、2或4-咪唑基、2或3-噁唑基、2或3-噁唑基、2或3-噻唑基、吡啶基、吗啉基(morpholyl)、硫代吗啉基(thiomorpholyl)和吡唑基，
C6-C14芳基，诸如苯基、1-萘基和2-萘基，优选苯基，
C7-C20烷芳基，优选C7-C16烷芳基，特别优选C7-C12烷苯基，例如2-甲基苯基、3-甲基苯基、4-甲基苯基、2-乙基苯基、3-乙基苯基和4-乙基苯基，
C7-C20芳烷基，优选C7-C16芳烷基，特别优选C7-C12苯烷基，例如苄基、1-苯基乙基、2-苯基乙基、3-苯基丙基、1-苯基丁基、2-苯基丁基、3-苯基丁基、4-苯基丁基，特别优选苄基、1-苯基乙基和2-苯基乙基。
所述基团可被C1-C4烷基、C1-C4烷氧基、C2-C4酰基、C2-C4酰氧基、苯氧基、C2-C8二烷氨基、卤素、硝基和/或氰基取代。
优选使用的结构式Ⅰ、Ⅱ或Ⅲ的脲化合物是在反应条件下呈现液体的那些，特别优选N,N’-二甲基亚乙基脲、N,N’-二甲基亚丙基脲、N,N,N’,N’-四丁基脲和N,N,N’,N’-四甲基硫脲、N-氯甲基-N’-氰甲基亚丙基脲、N-甲基-N’-乙基亚丙基脲、1,3-二甲基-1,3-二氢苯并咪唑-2-酮、1-甲基-3-苯基咪唑烷-2,4,5-三酮、1,3,4,6-四甲基-1,3,4,6-四氢咪唑并[4,5-d]咪唑-2,5-二酮和4-甲氧基-1-甲基-3-苯基咪唑烷-2-硫酮。
所述脲化合物可以直接使用，以其当氢卤酸的盐形式，例如盐酸盐，或以其与光气反应所得盐(Vilsmeier盐)形式使用。
适用本发明的醇主要是下列结构式的醇：
其中R9和R10可相同或不同，为氢、烷基、烯基、炔基、烷氧基、芳氧基、羟烷基、羟烯基或羟炔基。
在符合定义的醇中，从本发明工艺的理想产物出发，优选其中的R9和R10有下列含义的醇：
氢；
C1-C22烷基，优选C4-C18烷基，更优选C6-C10烷基，例如特别是正己基和正辛基；
C3-C22烯基，优选C4-C6烯基，例如特别是丁烯基；
C3-C22炔基，优选C3-C8炔基，例如特别是丙炔基；
C1-C22烷氧基，优选C1-C4烷氧基，例如特别是丙氧基；
单或双环的芳氧基，例如优选苯氧基，其中芳族环上也可能含有诸如氧、硫或氮的杂原子和/或被最多3个C1-C12烷基、卤素诸如氟、氯和溴或者C1-C4烷氧基取代；
C1-C16羟烷基，优选C2-C12羟烷基，更优选C4-C8羟烷基，例如特别是羟丁基、羟己基和羟辛基；
C1-C16羟烯基，优选C2-C12羟烯基，更优选C4-C8羟烯基，例如特别是羟丁烯基、羟己烯和羟辛烯基；
C1-C16羟炔基，优选C2-C12羟炔基，更优选C4-C8羟炔基，例如特别是羟丁炔基、羟己炔基和羟辛炔基。
除氢以外的这些基团可进一步被下列基团取代：优选C1-C4烷基，C1-C4酯，氰基，卤素如特别是氟、氯和溴，芳基如特别是苯基和4-甲氧基苯基，和芳氧基如优选苯氧基。
优选的醇是：
2-(4-甲氧基苯基)乙醇、2-乙基己醇、正辛醇、3-丁烯醇、炔丙醇、1,4-丁二醇、1,8-辛二醇，并且从本发明工艺的理想产物出发特别优选1,6-己二醇。
所用的氯化剂是本身已知的试剂，例如光气、亚硫酰氯和草酰氯，优选用光气。
通常优选另外使用氯化氢，其量优选为醇的5-100mol％优选20-40mol％。
本发明工艺可作为均匀催化的液相反应来实施。合适的液体反应介质是要被使用的伯、仲或叔醇或惰性溶剂或它们的混合物。适宜的惰性溶剂是芳族烃，如甲苯、二甲苯或苯，卤代烃，如四氯乙烷、氯苯或二氯苯，或酯如乙酸乙酯或乙酸丁酯。
本发明工艺可以连续或不连接地进行。本发明工艺优选连续进行，例如在搅拌罐，级联搅拌罐、环形反应器或逆流塔中。反应温度一般为-20至180℃，优选0至120℃，特别优选40至100℃。反应进行的压力一般为0.01-50bar，优选0.5-5bar，特别优选大气压。
脲化合物Ⅰ、Ⅱ和/或Ⅲ的用量一般为基于所用醇(Ⅳ)计的0.01-20mol％。催化剂的量也取决于反应是否就是在所用醇中或是在溶剂中进行。
脲化合物Ⅰ、Ⅱ和/或Ⅲ的用量优选为0.001-1mol％，特别优选0.002-0.1mol％，尤其优选0.005-0.05mol％。
氯化剂和醇(Ⅳ)的摩尔比一般为0.5∶1-50∶1。通常情况下使用过量的氯化剂，因为否则的话会剩下未反应的醇。氯化剂和醇(Ⅳ)的摩尔比优选为1∶1-2∶1，特别优选1∶1-1.5∶1，尤其是1∶1-1.2∶1。
氯化反应之后可进行一个或多个用于反应产物纯化的步骤。这样，合适时，从光气化反应中排出的液体可用机械分离法如澄清过滤将不溶杂质除去。这种机械分离步骤通常足以得到足够高纯度的产物，可省去进一步的加工处理。然而，可能要进行除去溶解性杂质的其它纯化步骤，例如蒸馏或重结晶。
含催化剂的蒸馏残余物可返回到反应中。
已知按本发明工艺经济地得到的烷基、烯基和炔基氯是有机合成中的有用中间体，特别是用于作物保护剂、电化学助剂和塑料前体。
本发明借助下列实施例进行说明：
实施例1-5
在120-130℃温度，bmol光气和2mol醇(Ⅳ)经5小时的时间加入到0.5mol具体的烷基氯和基于醇计0.001mol％的脲化合物的混合物中。接着混合物在反应温度下再保持1小时。用氮气将过量光气从混合物中驱除出去，这样得到的粗产物在澄清过滤后以气相色谱(GC)进行检测。
这些实验的细节见下表1。
实施例6
在120-130℃温度，bmol亚硫酰氯和2mol 1,4-丁二醇经历7小时的时间加到0.5mol 1,4-二氯丁烷和基于1,4-丁二醇计0.01mol％N,N’-二甲基亚丙基脲的混合物中。混合物在该反应温度下再保存1小时。用氮气将过量亚硫酰氯从混合物中驱除出去。这样得到的粗产物在澄清过滤后以气相色谱进行检测。
实验细节见下表1。
表1
| 实施例 | 醇 | 脲化合物 | 氯化剂b[mol] | GC分析[％] | ||
| 烷基氯 | 醇 | 氯甲酸酯 | ||||
| 1 | 1,4-丁二醇 | N,N’-二甲基亚丙基脲 | COCl2/1.05 | 98.6 | ＜0.01 | ＜0.01 |
| 2 | 1,4-丁二醇 | N,N,N’,N’-四丁基脲 | COCl2/1.05 | 95.6 | ＜0.01 | O.26 |
| 3 | 1,4-丁二醇 | N,N’-二甲基亚乙基脲 | COCl2/1.05 | 98.6 | ＜0.O1 | ＜O.01 |
| 4 | 1,4-丁二醇 | N,N,N’,N’-四甲基硫脲 | COCl2/1.05 | 98.3 | ＜0.00 | ＜0.04 |
| 5 | 1,4-己二醇 | N,N’-二甲基亚丙基脲 | COCl2/1.05 | 98.2 | 0.02 | ＜0.01 |
| 6 | 1,4-丁二醇 | N,N’-二甲基亚丙基脲 | SOCl2/1.05 | 98.4 | ＜0.01 | ＜0.01 |
Claims (6)
1．通过在催化剂存在下与氯化剂反应由醇制备烷基、烯基和炔基氯的工艺，其中催化剂是结构式(Ⅰ)的脲化合物：
R1R2N-CX-NR3R4 (Ⅰ)其中基团R1、R2、R3和R4可相同或不同，相互独立地是未取代或被1-3个C1-C4烷氧基、C2-C4酰基、C2-C4酰氧基、苯氧基、C2-C8二烷氨基、卤素、硝基和/或氰基取代的C1-C20烷基，C2-C12烯基，C2-C12炔基或者未取代或被1-3个C1-C4烷基、C1-C4烷氧基、C2-C4酰基、C2-C4酰氧基、苯氧基、C2-C8二烷氨基、卤素、硝基和/或氰基取代的C3-C12环烷基，C4-C12烷基环烷基，C4-C12环烷基烷基，杂环烷基，C5-C20杂环烷基烷基，C6-C14芳基，C7-C20芳烷基或C7-C20烷芳基，或其中基团R1或R2中的一个与基团R3或R4中的一个共同是未取代的或被1-3个C1-C4烷基、C1-C4烷氧基、C2-C4酰基、C2-C4酰氧基、苯氧基、C2-C8二烷氨基、卤素、硝基和氰基取代的C2-C12亚烷基链，该链可被醚、硫醚、叔氨基、酮、内酯、N-烷基取代的内酰胺或砜基团所中断，和其中X是氧或硫原子，和/或是通式(Ⅱ)的脲化合物：
其中X有上述的含义，R5、R6、R7和R8可相同或不同，相互独立地具有对R1-R4给出的含义，
和/或是通式(Ⅲ)的化合物：其中X、R5-R8具有上述的含义，Z1、Z2可相同或不同，是未取代的或被1-3个C1-C4烷基、C1-C4烷氧基、C2-C4酰基、C2-C4酰氧基、苯氧基、C2-C8二烷氨基、卤素、硝基和/或氰基取代的亚甲基，亚乙基或亚乙烯基。
2．根据权利要求1的工艺，其中催化剂是N,N’-二甲基亚乙基脲、N,N’-二甲基亚丙基脲、N,N,N’,N’-四丁基脲和N,N,N’,N’-四甲基硫脲、N-氯甲基-N’-氰甲基亚丙基脲、N-甲基-N’-乙基亚丙基脲、1,3-二甲基-1,3-二氢苯并咪唑-2-酮、1-甲基-3-苯基咪唑烷-2,4,5-三酮、1,3,4,6-四甲基-1,3,4,6-四氢咪唑并[4,5-d]咪唑-2,5-二酮和4-甲氧基-1-甲基-3-苯基咪唑烷-2-硫酮。
3．根据权利要求1或2的工艺，其中结构式Ⅱ的醇是下式的化合物：
其中R9和R10为氢、烷基、烯基、炔基、烷氧基、芳氧基、羟烷基、羟烯基或羟炔基。
4．根据权利要求1-3任一项的工艺，其中脲化合物的用量为0.0001-1mol％，基于醇计。
5．根据权利要求1-4任一项的工艺，其中反应在-40至100℃温度和大气压力下进行。
6．根据权利要求1-5任一项的工艺，其中反应在溶剂存在下进行。
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| DE19824929A DE19824929A1 (de) | 1998-06-04 | 1998-06-04 | Verfahren zur Herstellung von Alkyl-, Alkenyl- und Alkinylchloriden |
| DE19824929.2 | 1998-06-04 |
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| CN1304393A true CN1304393A (zh) | 2001-07-18 |
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| JP (1) | JP2002516886A (zh) |
| KR (1) | KR20010052528A (zh) |
| CN (1) | CN1304393A (zh) |
| DE (2) | DE19824929A1 (zh) |
| ES (1) | ES2205829T3 (zh) |
| WO (1) | WO1999062848A1 (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819473A (zh) * | 2013-07-01 | 2014-05-28 | 江阴摩尔化工新材料有限公司 | 一种甘脲树脂及其制备方法 |
| CN107118073A (zh) * | 2017-05-10 | 2017-09-01 | 武汉桀升生物科技有限公司 | 二醇催化制备二氯卤代烷的方法 |
| CN110330405A (zh) * | 2019-08-02 | 2019-10-15 | 昆山力田医化科技有限公司 | 一种1,4-二氯丁烷生产工艺 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7411131B2 (en) * | 2006-06-22 | 2008-08-12 | Adc Telecommunications, Inc. | Twisted pairs cable with shielding arrangement |
| DE102010055499A1 (de) * | 2010-12-22 | 2011-06-16 | W.C. Heraeus Gmbh | Prozess zur Herstellung von Bendamustinalkylester, Bendarmustin sowie Derivaten davon |
| JP6761211B2 (ja) * | 2016-09-02 | 2020-09-23 | 日産化学株式会社 | チオグリコールウリル類及びその製造方法 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3927106A (en) * | 1971-02-16 | 1975-12-16 | Quaker Oats Co | Preparation of tetrachlorocyclo-hexanone |
| FR2495610A1 (fr) * | 1980-12-05 | 1982-06-11 | Poudres & Explosifs Ste Nale | Procede de fabrication de thiochloroformiates |
| US5241086A (en) * | 1989-05-02 | 1993-08-31 | Rhone-Poulenc Chimie | Process for the preparation of brominated compounds, especially from alcohols |
| DE4116365A1 (de) * | 1991-05-18 | 1992-11-19 | Basf Ag | Verfahren zur herstellung von alkyl-, alkenyl- und alkinylchloriden |
| DE4332336A1 (de) * | 1993-09-23 | 1995-03-30 | Basf Ag | Verfahren zur Herstellung von Alkylchloriden |
| DE19737619A1 (de) * | 1997-08-28 | 1999-03-04 | Basf Ag | Verfahren zur Herstellung von Thiochlorformiaten |
-
1998
- 1998-06-04 DE DE19824929A patent/DE19824929A1/de not_active Withdrawn
-
1999
- 1999-05-21 ES ES99925022T patent/ES2205829T3/es not_active Expired - Lifetime
- 1999-05-21 KR KR1020007013672A patent/KR20010052528A/ko not_active Application Discontinuation
- 1999-05-21 JP JP2000552063A patent/JP2002516886A/ja not_active Withdrawn
- 1999-05-21 DE DE59906364T patent/DE59906364D1/de not_active Expired - Lifetime
- 1999-05-21 WO PCT/EP1999/003489 patent/WO1999062848A1/de not_active Application Discontinuation
- 1999-05-21 EP EP99925022A patent/EP1084091B1/de not_active Expired - Lifetime
- 1999-05-21 US US09/700,746 patent/US6245954B1/en not_active Expired - Fee Related
- 1999-05-21 CN CN99806950A patent/CN1304393A/zh active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819473A (zh) * | 2013-07-01 | 2014-05-28 | 江阴摩尔化工新材料有限公司 | 一种甘脲树脂及其制备方法 |
| CN107118073A (zh) * | 2017-05-10 | 2017-09-01 | 武汉桀升生物科技有限公司 | 二醇催化制备二氯卤代烷的方法 |
| CN110330405A (zh) * | 2019-08-02 | 2019-10-15 | 昆山力田医化科技有限公司 | 一种1,4-二氯丁烷生产工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2205829T3 (es) | 2004-05-01 |
| DE19824929A1 (de) | 1999-12-09 |
| EP1084091A1 (de) | 2001-03-21 |
| WO1999062848A1 (de) | 1999-12-09 |
| KR20010052528A (ko) | 2001-06-25 |
| JP2002516886A (ja) | 2002-06-11 |
| DE59906364D1 (de) | 2003-08-28 |
| US6245954B1 (en) | 2001-06-12 |
| EP1084091B1 (de) | 2003-07-23 |
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