CN1329358C - 3,3′,5,5′,6,6′-六烷基-2,2′-联苯酚、3,3′,4,4′,5,5′-六烷基-2,2-联苯酚和3,3′,4,4′,5,5′,6,6′-八烷基-2,2′-联苯酚的制备方法 - Google Patents
3,3′,5,5′,6,6′-六烷基-2,2′-联苯酚、3,3′,4,4′,5,5′-六烷基-2,2-联苯酚和3,3′,4,4′,5,5′,6,6′-八烷基-2,2′-联苯酚的制备方法 Download PDFInfo
- Publication number
- CN1329358C CN1329358C CNB028273540A CN02827354A CN1329358C CN 1329358 C CN1329358 C CN 1329358C CN B028273540 A CNB028273540 A CN B028273540A CN 02827354 A CN02827354 A CN 02827354A CN 1329358 C CN1329358 C CN 1329358C
- Authority
- CN
- China
- Prior art keywords
- compound
- xenol
- gained
- phenol
- tetramethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 21
- -1 copper halide salt Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 11
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 10
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 claims description 2
- UNEXJVCWJSHFNN-UHFFFAOYSA-N n,n,n',n'-tetraethylmethanediamine Chemical compound CCN(CC)CN(CC)CC UNEXJVCWJSHFNN-UHFFFAOYSA-N 0.000 claims description 2
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 claims description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 51
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- 239000000243 solution Substances 0.000 description 47
- 239000000203 mixture Substances 0.000 description 35
- 238000002360 preparation method Methods 0.000 description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 22
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- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 150000004699 copper complex Chemical class 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- OSDLLIBGSJNGJE-UHFFFAOYSA-N 4-chloro-3,5-dimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1Cl OSDLLIBGSJNGJE-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000005844 Thymol Substances 0.000 description 4
- 239000012080 ambient air Substances 0.000 description 4
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- 238000001953 recrystallisation Methods 0.000 description 4
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Natural products CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 4
- 229960000790 thymol Drugs 0.000 description 4
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- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- 239000000706 filtrate Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000003822 preparative gas chromatography Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
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- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- AQZMINLSVARCSL-UHFFFAOYSA-N 4-chloro-3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile Chemical compound ClC1=CC(=O)C(C#N)=C(C#N)C1=O AQZMINLSVARCSL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-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
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
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- JRQJLSWAMYZFGP-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical class OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 JRQJLSWAMYZFGP-UHFFFAOYSA-N 0.000 description 1
- QPVRKFOKCKORDP-UHFFFAOYSA-N 1,3-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC(C)(O)CC=C1 QPVRKFOKCKORDP-UHFFFAOYSA-N 0.000 description 1
- PXSSNPBEHHJLDH-UHFFFAOYSA-N 2,3,4,5-tetramethylphenol Chemical compound CC1=CC(O)=C(C)C(C)=C1C PXSSNPBEHHJLDH-UHFFFAOYSA-N 0.000 description 1
- IYOQRPVGIYXSKV-UHFFFAOYSA-N 2-cyclohexyl-4,5-dimethylphenol Chemical compound C1=C(C)C(C)=CC(O)=C1C1CCCCC1 IYOQRPVGIYXSKV-UHFFFAOYSA-N 0.000 description 1
- CSRYWUMVSWOHET-UHFFFAOYSA-N 4-cyclohexyl-2,5-dimethylphenol Chemical compound C1=C(O)C(C)=CC(C2CCCCC2)=C1C CSRYWUMVSWOHET-UHFFFAOYSA-N 0.000 description 1
- PRLINSMUYJWPBL-UHFFFAOYSA-N 4-tert-butyl-2-chlorophenol Chemical compound CC(C)(C)C1=CC=C(O)C(Cl)=C1 PRLINSMUYJWPBL-UHFFFAOYSA-N 0.000 description 1
- SNKLPZOJLXDZCW-UHFFFAOYSA-N 4-tert-butyl-2-methylphenol Chemical compound CC1=CC(C(C)(C)C)=CC=C1O SNKLPZOJLXDZCW-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical group ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical class NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 125000005538 phosphinite group Chemical group 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- SWWHCQCMVCPLEQ-UHFFFAOYSA-N propan-2-yl methanesulfonate Chemical compound CC(C)OS(C)(=O)=O SWWHCQCMVCPLEQ-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical class CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- QUJLPICXDXFRSN-UHFFFAOYSA-N scandium;trifluoromethanesulfonic acid Chemical compound [Sc].OS(=O)(=O)C(F)(F)F QUJLPICXDXFRSN-UHFFFAOYSA-N 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- GNBVPFITFYNRCN-UHFFFAOYSA-M sodium thioglycolate Chemical compound [Na+].[O-]C(=O)CS GNBVPFITFYNRCN-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
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Abstract
一种制备式(I)化合物的方法,所述方法为在含氧分子气体和含铜催化剂的存在下,将式(II)化合物氧化偶合成式(I)化合物;所述含铜催化剂由铜卤盐与有机二胺化合物接触制得。同时还要求保护某些式(I)化合物。
Description
本发明领域
本发明涉及制备:
3,3’,4,4’,5,5’,6,6’-八烷基-2,2’-联苯酚、3,3’,4,4’,5,5’-六烷基-2,2’-联苯酚以及3,3’,5,5’,6,6’-六烷基-2,2’-联苯酚的方法。
本发明背景
取代联苯酚化合物,例如3,3’,6,6’-四烷基-2,2’-联苯酚、3,3’,4,4’,5,5’-六烷基-2,2’-联苯酚、3,3’,4,4’,5,5’,6,6’-八烷基-2,2’-联苯酚、3,3′,5,5’,6,6’-六烷基-2,2’-联苯酚、3,3’,5,5’-四烷基-2,2’-联苯酚、3-烷基-5,5’,6,6’7,7’,8,8’-八氢-2,2’-联萘酚、3,3’-二烷基-5,5’,6,6’,7,7’,8,8’-八氢-2,2’-联萘酚和3,3’,6,6’-四烷基-5,5’-二卤-2,2’-联苯酚,可用于制备以磷为基础的催化剂配体。这类配体包括膦、次亚膦酸酯(phosphinites)、亚膦酸酯以及亚磷酸酯。单(磷)配体为含单个磷原子的化合物,所述磷原子作为过渡金属的供体。而双(磷)配体通常含有两个磷供体原子,而且通常与过渡金属形成环状螯合物结构。
一般来说,联苯酚可通过氧化偶合(单)酚制备,但常常同时得到其它类型产物如酮,和/或因为不同原因而整体收率低。
可通过使用多种氧化剂如硝酸、氯化铁、铁氰化钾、铬酸、2,3-二氯-5,6-二氰基苯醌和二叔丁基过氧化物,将酚氧化偶合制成相应的联苯酚。2,2’-二羟基-3,3’-二-异丙基-6,6’-二甲基联苯可用2-异丙基-5-甲基-酚与2,3-二氯-5,6-二氰基苯醌或二-t-丁基过氧化物制备。参见Tetrahedron,1875,1971;J.Chem.Soc.,Perkin Trans.II,587,1983。部分所述氧化剂和/或助催化剂涉及到使用相对昂贵和/或爆炸性(过氧化物)的化合物,其妨碍大规模商业化使用。
利用过渡金属催化剂和氧化剂组合,如过硫酸阴离子或氧,酚也可被氧化偶合。参见美国专利6,077,979、4139,544、4,132,722、4,354,048和4,108,908;J.Org.Chem.1984,49,4456和J.Org.Chem1983,48,4948。所引用的专利公开了作为氧化剂的氧与各种催化性铜络合物如亚铬酸铜、乙酸铜和巯基乙酸钠、乙酸铜和二亚乙基三胺五乙酸五钠、以及乙酸铜与1,3-二氨基-2-羟基丙烷-四乙酸的用法。所述专利的实施例公开了使用2,6-二取代酚或2,4-二-叔-丁基酚。
铜胺催化剂与氧化剂氧在与2,4-二-叔-丁基酚、2-甲基-4-叔-丁基酚、2-氯-4-叔-丁基酚和4-叔-丁基酚有关的氧化偶合中的用途已有介绍,参见J.Org.Chem.1984,49,4456和J.Org.Chem.1983,48,4948。
本领域一直需要以适当产率制备取代联苯酚的方法,所述联苯酚适用于制备以磷为基础的催化剂配体。
本发明概述
在第一方面,本发明为制备下式化合物的方法,
包括以下步骤:
在含氧分子气体和含铜催化剂存在下,氧化偶合下式化合物,
所述含铜催化剂通过含铜卤盐与有机二胺化合物接触的方法制得,
其中:
R1为C1-C6(伯、仲或环)烷基;
R2为氢、C1-C6(伯、仲、叔或环)烷基;
R3为C1-C6(伯、仲、叔或环)烷基;
R4为氢、C1-C6(伯、仲或环)烷基,
前提条件是R2和R4不同时为氢。
在第二方面,本发明为下式化合物,
其中:
R1为甲基、乙基、n-丙基或异丙基;
R2为氢或甲基;
R3为甲基、乙基、n-丙基、异丙基或t-丁基;以及
R4为甲基;
前提条件是如果R1为异丙基而R2为氢,则R3不为甲基。
优选化合物为以上介绍的化合物,其中:
R1为甲基或异丙基;
R2为氢或甲基;
R3为甲基、异丙基或t-丁基;以及
R4为甲基。
最优选化合物为上一段的化合物,其中:
R1为异丙基;
R2为氢;
R3为异丙基;以及
R4为甲基。
本发明详述
本发明提供制备3,3’,5,5’,6,6’-六烷基-2,2’-联苯酚、3,3’,4,4’,5,5’-六烷基-2,2’-联苯酚或3,3’,4,4’,5,5’,6,6’-八烷基-2,2’-联苯酚的方法,该方法为用铜胺催化剂和氧化剂氧分别与2,4,5-三烷基酚、2,3,4-三烷基酚或2,3,4,5-四烷基酚氧化偶合。适合的酚由下式代表:
其中
R1为C1-C6(伯、仲或环)烷基;
R2为氢、C1-C6(伯、仲、叔或环)烷基;
R3为C1-C6(伯、仲、叔或环)烷基;
R4为氢、C1-C6(伯、仲或环)烷基;
前提条件是R2和R4不同时为氢。
所述烷基基团可相互连接或不连接。例如烷基基团R1和R2,可连接形成稠合的环烷基基团。同样,烷基基团R2和R3;或R3和R4可连接形成稠合的环烷基基团。一些代表性的2,4,5-三烷基酚、2,3,4-三烷基酚和2,3,4,5-四烷基酚如下式所示。
通过氧化偶合使2,4,5-三烷基酚、2,3,4-三烷基酚、2,3,4,5-四烷基酚或2,4-二烷基酚二聚合成相应的联苯酚。无溶剂或在一种或多种宽范围的难以被氧化的溶剂存在下,进行氧化偶合,所述溶剂包括二氯甲烷、氯苯、甲苯、二甲苯、硝基甲烷、石蜡等。含氧分子气体用作氧化剂。例如静态空气、流动空气或氧气可用于氧化偶合。所述反应通常在惰性溶剂中将酚与二胺铜络合物接触进行,优选非质子溶剂,例如二氯甲烷、甲苯、氯苯或饱和烃,优选其中闪点高于反应温度的溶剂,反应温度在5-100℃之间,优选在30℃左右。通常用饱和烃溶剂稀释、过滤,并任选用水性矿物酸或铜螯合试剂如EDTA钠洗涤纯化分离所得的产物。所得联苯酚可任选通过重结晶纯化。
铜二胺催化剂可按Tetrahedron Letters,1994,35,7983介绍的方法制备。将铜卤化物例如CuCl、CuBr、CuI、CuCl2加入到醇(例如甲醇)和水的混合物;再缓慢加入所述二胺。加入二胺后,向所得混合物中喷入空气并剧烈搅拌。将所得催化剂过滤。浓缩滤液,过滤需要的催化剂还可以获得一些催化剂。所述催化剂也可通过将铜卤化物与所述二胺在用于偶合反应的溶剂中接触原位制备。二胺的实例包括但不限于以下化合物:
N,N,N’,N’-四乙基乙二胺、N,N,N’,N’-四乙基-1,3-丙二胺、N,N,N’N’-四乙基甲二胺、N,N,N’,N’-四甲基-1,6-己二胺、N,N,N’,N’-四甲基-1,3-丙二胺、二哌啶子基甲烷、N,N,N’,N’-四甲基乙二胺和1,4-二氮杂双环-(2,2,2)-辛烷。优选所述二胺为N,N,N’,N’-四取代乙二胺或丙二胺或甲二胺,例如四甲基乙二胺(TMEDA)、N,N,N’,N’-四乙基-1,3-丙二胺和N,N,N’,N’-四乙基甲二胺。由本发明方法制备的3,3’,5,5’,6,6’-六烷基酚可用于制备聚合配体,其制备方法包括:(1)在Lewis酸催化剂的存在下,通过将本发明方法制备的3,3’,5,5’,6,6’-六烷基酚与含苄基氯基团的聚合物反应,(2)在有机碱的存在下,将步骤(1)的产物与至少一种偶磷酰氯(phosphorochloridite)化合物反应。优选Lewis酸催化剂为氯化铝,而有机碱为三烷基胺。
本发明的联苯酚可用于制备双配位基亚磷酸化合物。使用联苯酚制备双配位基亚磷酸化合物方法在美国专利5,235,113、6,031,120和6,069,267中有介绍,将其公开的方法通过引用结合到本文。利用双配位基亚磷酸化合物的两个重要的工业制备方法是烯属化合物的氢氰化和加氢甲酰基化。双配位基亚磷酸化合物经证实可用于单烯属化合物和二烯属化合物的氢氰化以及用于使非共轭2-烷基-3-单烯腈(monoalkenenitriles)异构化为3-和/或4-单烯。例如,参见美国专利5,512,695、5,512,696以及国际专利申请WO9514659。双配位基亚磷酸配体已显示可用于烯属加氢甲酰基化反应。例如参见美国专利5,235,113。
本发明还涉及下式化合物:
其中:
R1为甲基、乙基、n-丙基或异丙基;
R2为氢或甲基;
R3为甲基、乙基、n-丙基、异丙基或t-丁基;及
R4为甲基;
前提条件是如果R1为异丙基而R2为氢,则R3不为甲基。
优选化合物为上述介绍的化合物,其中:
R1为甲基或异丙基;
R2为氢或甲基;
R3为甲基、异丙基或t-丁基,以及
R4为甲基。
最优选的化合物为前一段的化合物,其中:
R1为异丙基;
R2为氢;
R3为异丙基;以及
R4为甲基。
实施例
用以下非限制性实施例阐述本发明。
实施例1
5,5’-二(t-丁基)-3,3’,6,6’-四甲基-2,2’-联苯酚的制备
在18.6g(0.104mol)4-t-丁基-2,5-二甲苯酚的20ml二氯甲烷溶液中加入0.6g(3mmol)的羟氯-TMEDA合铜络合物(TMEDA=四甲基乙二胺)。将所得的深紫色混合物在环境空气中搅拌过夜。气相色谱(GC)分析显示仅有25%转化,所以将所述混合物用二氯甲烷稀释,(MgSO4)干燥,再浓缩至干。将20ml环己烷以及1.2g(6mmol)上述羟氯-TMEDA合铜催化剂加入所得粗残余物,将所得混合物在空气和环境温度下搅拌3天(85%转化)。将所得的紫色溶液浓缩至干,然后将所得的残余物在硅胶上色谱分离,得到10.2g(55%)纯的5,5’-二(t-丁基)-3,3’,6,6’-四甲基-2,2’-联苯酚,mp103-105℃。1H-NMR(CDCl3)1.42,(s,9H),2.06(s,3H),2.25(s,3H),4.54(s,1H),6.51(s,1H),7.24(s,1H)。
实施例2
5,5’-二-t-丁基-3,3’-二-异丙基,6,6’-二甲基-2,2’-联苯酚的制备
在20g(0.104mol)4-t-丁基百里酚的50ml二氯甲烷溶液中加入1.0g(5mmol)羟氯-TMEDA合铜络合物,将所得的深紫色混合物在环境空气中搅拌3天(50%转化)。所得混合物用己烷稀释,用EDTA水溶液洗涤,(MgSO4)干燥,然后浓缩至干。将所得的残余物在硅胶上色谱分离,得到3.6g(34%,按转化计)的纯5,5’-二-t-丁基-3,3’-二-异丙基,6,6’-二甲基-2,2’-联苯酚二聚物,mp105-108℃。1H-NMR(CDCl3)δ126(d,6H),(s,9H),3.25(septet,1H),4.58(s,1H),7.30(s,1H)。
实施例3
3,3’,4,4’,5,5′,6,6’-八甲基-2,2’-联苯酚的制备
2,3,4,5-四甲基酚的制备
在纯度为85%的56g 5-溴连四甲苯(0.22mol)(按照J.Am.Chem.Soc.1929,3001制备;用乙酸代替氯仿作溶剂,使用1wt%的铁粉,环境温度,分级蒸馏所述产物)的50ml二甘醇二甲醚溶液中加入1.0g的2-氨基吡啶、1.1g氯化亚铜和80g 25%甲醇钠甲醇溶液,在氮气下将所述混合物加热除去甲醇。经120℃加热16小时后,转化率为60%,再加入0.7g氨基吡啶、1.0gCuCl以及20g甲醇钠溶液。经100℃、4小时反应后,转化率为90%。将所得混合物冷却,用200ml己烷和100ml的3%氨水稀释混合物,将所得有机相用水洗涤,(MgSO4)干燥,再浓缩至干。然后将得到的5-甲氧基连四甲苯(43.1g)粗品与130ml的48%HBr水溶液一起在100℃加热2天,用水和己烷稀释,冷却至5℃,过滤所得固体并用冷水和己烷洗涤。在真空中干燥,得到22g 2,3,4,5-四甲基酚。另从滤液中回收到4.5g所述化合物,共计26.5g(80%,以溴化物计)。1H-NMR(CDCl3)δ2.12(s,3H),2.16(s,3H),2.19(s,3H),2.21(s,3H),4.44(s,1H),648(s,1H)。2,3,4,5-四甲基酚的二聚合
在空气和环境温度下,将所述单体(2.6g,17.3mmol)和10ml甲苯、0.15g(6.3mmol)Cu(OH)Cl-TMEDA一起搅拌6小时(转化85%)。所得混合物用5ml HCl(1N)和20ml己烷稀释,搅拌15分钟,过滤。将所得固体与第二次从滤液中回收的小量收得物合并,抽气干燥,得到1.4g(54%)八甲基-2,2’-联苯酚,mp202℃。1H-NMR(CDCl3)δ1.90(s,3H),2.20(s,3H),2.22(s,3H),2.26(s,3H),4.60(s,1H)。
实施例4:
3,3’-二异丙基-5,5’,6,6’-四甲基-2,2’-联苯酚的制备
在15.0g(0.0915mol)4-甲基百里酚的15ml二氯甲烷溶液中加入0 75g(3.2mmol)羟氯-TMEDA合铜络合物。在环境温度下,将所得溶液搅拌暴露于空气4-6小时。将所得混合物与5ml饱和EDTA二钠水溶液一起搅拌10分钟以分解铜络合物,然后用80ml己烷稀释,将己烷层浓缩至干。将所得粗品在己烷中重结晶,得到两部分产物,共计8.5g(63%收率,按90%转化率计),1H-NMR(CDCl3)δ1.24(d,6H,J=7Hz),1.87(s,3H),2.26(s,3H),3.26(septet,1H,J=7Hz),4.6(s,1H),7.06(s,1H)。第一部分产物的mp107℃(参考文献:美国专利4880775:mp 106-107.5℃)。
大规模制备:
在2-异丙基-4,5-二甲基酚(140g,0.85mol)的140ml二氯甲烷溶液中加入羟氯-TMEDA合铜络合物(5g)。在环境温度下,向所得溶液中通入空气,同时搅拌20小时。在室温下,将所得混合物用EDTA二钠处理30分钟,然后用己烷(50ml)稀释,再用水和HCl(0.5N)洗涤。将所得溶液浓缩,得到残余物,所得残余物用色谱进一步纯化,得到2-异丙基-4,5-二甲基酚二聚体(80g,57%)。另得到5g不纯的产物。
1H NMR 1.28(d,J=7Hz,12H),1.90(s,6H),2.30(s,6H),3.29(septet,J=7Hz,2H),4.63(s,2H),7.08(s,2H)ppm。13C NMR 16,0,19.90,22.5,22.7,27.1,122.2,128.16,128.6,132.0,133.6,148.9ppm。
实施例5
3,3’-二异丙基-5,5’-二乙基-6,6’-二甲基-2,2’-联苯酚的制备
在23.5g 4-乙基百里酚的50ml甲苯溶液中加入1.2g Cu(OH)Cl-TMEDA,在环境空气中将所得混合物搅拌18小时(90%转化,6小后转化80%)。所得产物按上述方法后续处理,并用色谱(SiO2/己烷)分离,得到10.0g(42%)的二聚体,通过气相分析约为95%纯度,mp61-64℃。1H-NMR(CDCl3)δ1.2(m,9H),1.88(s,3H),2.62(q,2H,J=7.5Hz),3.27(septet,1H),4.61(s,1H),7.07(s,1H)。
实施例6
3,3’,5,5’,6,6’-六甲基-2,2’-联苯酚的制备
在2,4,5-三甲基酚(1.9g)的4ml二氯甲烷溶液中加入羟氯-TMEDA合铜络合物(0.2g)。在所得溶液中鼓泡通入空气,同时在环境温度下搅拌45小时。所得混合物用乙醚稀释,再分别用HCl(2N)和水洗涤。所得乙醚溶液用GC分析,GC分析指出转化率为95%,选择性为72%。
铜催化的2,4,5-三甲基酚偶合
a)催化剂溶液
在缺氧环境下,将0.550g 2,4,5-三甲基酚的10mlCH2Cl2溶液与0.924(TMEDA)CuCl(OH)混和,制成深蓝色溶液。
b)偶合:
在26.6g 2,4,5-三甲基酚的125ml CH2Cl2溶液中加入2ml下述(a)的铜催化剂溶液。在环境温度下,向所得溶液上方缓慢通入空气流并同时搅拌。在19小时、34小时后,分别再加入2ml、3ml催化剂溶液。催化剂与2,4,5-三甲基酚的克分子比为1.4%。经2d GC分析显示选择性为98%的转化99%。将所得反应混合物降至0℃,滤出产物并用小量CH2Cl2洗涤,得到16.5g 3,3’,5,5’,6,6’-六甲基-2,2’-联苯酚。另从母液中分离出6.2g 3,3’,5,5’,6,6’-六甲基-2,2′-联苯酚。通过GC和NMR分析,分离出的产物的纯度为99%。1H nmr(CDCl3):δ6.93(s,2H),4.49(s,2H),2.17(s,12H),1.76(s,6H)。
实施例7
3,3’-二环己基-5,5’,6,6’-四甲基-2,2’-联苯酚的制备
在2-环己基-4,5-二甲基酚(4.5g,22mmol)的25ml二氯甲烷溶液中加入羟氯-TMEDA合铜络合物(45mg)。在所得溶液中鼓泡通入空气,同时在环境温度下将溶液搅拌3小时。所得混合物用乙醚稀释并分别用HCl(2N)和水洗涤。然后浓缩所述乙醚溶液,得到残余物,所述残余物再用色谱进一步纯化,得到起始物2-环己基-4,5-二甲基酚(1.35g)和3,3’-二环己基-5,5’,6,6’-四甲基-2,2’-联苯酚(1.8g,57%,按消耗的2-环己基-4,5-二甲基酚计)。1H NMR 1.27(m,2H),1.39(m,8H),1.75(m,2H),1.84(s,6H),1.86(m,8H),2.22(s,6H),2.85(m,2H),4.52(s,2H),7.04(s,2H)ppm。13C NMR 16.1,19.9,26.5,27.1,33.2,37.3,120.2,128.6,129.6,131.3,133.6,148.8ppm。
实施例8
3,3’-二环戊基-5,5’,6,6’-四甲基-2,2’-联苯酚的制备
在2-环戊基-4,5-二甲基酚(3.9g,21mmol)的10ml二氯甲烷溶液中加入羟氯-TMEDA合铜络合物(40mg)。在所得溶液中通入空气,同时将溶液在环境温度下搅拌3小时。在反应开始后1小时、2小时各加入(40mg)所述催化剂。所得混合物用二氯甲烷(50ml)稀释,再用HCl(0.5N)和水洗涤。然后浓缩所得溶液,得到残余物,用色谱进一步纯化残余物,得到3,3’-二环戊基-5,5’,6,6’-四甲基-2,2’-联苯酚(2.5g,64%)。1H NMR 1.71(m,8H),1.83(m,4H),1.89(s,6H),2.05(m,4H),2 29(s,6H),3.30(quintet,J=7Hz,2H),4.61(s,2H),7.12(s,2H)ppm。13CNMR 16.0,19.9,25.5,32.9,39.3,120.2,128.5,128.9,129.5,133.7,149.5ppm。
实施例9
3,3’-二-仲-丁基-5,5’,6,6’-四甲基-2,2’-联苯酚的制备
在2-仲-丁基-4,5-二甲基酚(1.3g,7.3mmol)的10ml二氯甲烷溶液中加入羟氯-TMEDA合铜络合物(10mg)。在所得溶液中通入空气,同时在环境温度下搅拌3小时。在反应开始后1小时、2小时各加入(10mg)所述催化剂。所得混合物用二氯甲烷(50ml)稀释,再用HCl(0.5N)和水洗涤。然后浓缩所得溶液,得到残余物,残余物用色谱进一步纯化,得到3,3’-仲-丁基-5,5’,6,6’-四甲基-2,2’-联苯酚(0.45g,35%)。1H NMR 0.87(m,6H),1.21(d,J=7Hz,6H),1.65(m,4H),1.85(m,6H),2.26(s,6H),3.01(m,2H),4.57(s,2H),7.02(s,2H)ppm。13CNMR 14.2&14.3,17.9&18.0,21.9,22.1,31.4&32.0,35.5,36.0,121.9,130.6,130.9,132.8,135.6,151.2ppm。
实施例10
3,3’,6,6’-四甲基-5,5’-二仲-丁基-2,2’-联苯酚的制备
在4-仲-丁基-2,5-二甲基酚(3.9g,22mmol)的4ml二氯甲烷溶液中加入羟氯-TMEDA合铜络合物(40mg)。在所得溶液中通入空气,同时在环境温度下搅拌3小时。在反应开始后1小时、2小时各加入所述催化剂(40mg)。所得混合物用二氯甲烷(40ml)稀释,并用HCl(0.5N)和水洗涤。然后浓缩所得溶液,得到残余物,所述残余物用色谱进一步纯化,并在冷己烷中重结晶,得到3,3’,6,6’-四甲基-5,5’-二-仲-丁基-2,2’-联苯酚(2.1g,54%)。1H NMR 0.87(m,6H),1.25(d,J=7Hz,6H),1.65(m,4H),1.91(m,6H),2.30(s,6H),2.91(m,2H),4.68(2s,2H),7.10(s,2H)ppm。13C NMR 11.9&12.0,14.90&14.97&15.03&15.09,15.7,21.0&21.1,30.49&30.52&30.74&30.77,35.6&35.7,119.8,121.3,128.0,132.51&132.55&132.59&132.64,137.8,149.0ppm。
实施例11
3,3’,5,5’-四异丙基-6,6’-二甲基-2,2’-联苯酚的制备
在2,4-二异丙基-5-甲基酚(50.0g,0.26mol)的50ml二氯甲烷溶液中加入羟氯-TMEDA合铜络合物(5.0g)。在所得溶液中通入空气,同时在环境温度下搅拌18小时。所得混合物用HCl(1.0N)洗涤,再用己烷萃取。将萃取液浓缩,得到残余物,残余物用色谱进一步纯化,得到20g(40%)的3,3’,5,5’-四异丙基-6,6’-二甲基-2,2’-联苯酚。1H NMR1.31(m,24H),1.98(s,6H),3.15(m,2H),3.33(m,2H),4.64(s,2H),7.15(s,2H)ppm。13C NMR 17.1,24.5 & 24.6,25.5 & 25.7,29.6,31.4,122.5,125.1,134.1,134.2,141.1,150.6ppm。
实施例12
3,3’-二-异丙基-5,5’-二环己基-6,6’-二甲基-2,2’-联苯酚的制备
在4-环己基-2-异丙基-5-甲基酚(1.8g,7.8mmol)的10ml二氯甲烷溶液中加入羟氯-TMEDA合铜络合物(20mg)。在所得溶液中通入空气溶液,同时在环境温度下搅拌3小时。在反应开始后1小时、2小时各加入所述催化剂(20mg)。所得混合物用二氯甲烷(50mL)稀释,再用HCl(0.5N)和水洗涤。然后浓缩所得溶液,得到残余物,残余物用色谱进一步纯化,得到3,3’-二-异丙基-5,5’-二环己基-6,6’-二甲基-2,2’-联苯酚(1.04g,58%)。1H NMR 1.24(d,J=7Hz,12H),1.27(m,2H),1.39(m,8H),1.78(m,10H),1.85(s,6H),2.68(m,2H),2.29(s,6H),3.25(hept,J=7Hz,2H),4.60(s,2H),7.12(s,2H)ppm。13C NMR 15.1,22.5,22.7,26.4,27.3,27.5,34.0 & 34.3,40.3,120.6,123.8,131.9,132.3,138.3,148.6ppm。
实施例13
3,3’,6,6’-四甲基-5,5’-二-环己基-2,2’-联苯酚的制备
在2,5-二甲基-4-环己基酚(21g,0.10mol)、羟氯-TMEDA合铜络合物(2.1g)和二氯甲烷(80mL)的混合物中通入空气,同时在环境温度下搅拌6小时。所得混合物用HCl(0.5N)洗涤,再用己烷萃取。将萃取液浓缩并干燥,得到残余物(20g,其含90%的产物:4-环己基-2,5-二甲基酚)。将残余物在己烷中重结晶,得到3,3’,6,6’-四甲基-5,5’-二-环己基-2,2’-联苯酚(6.5g,31%产率)。1H NMR(CDCl3):1.32(m,4H),1.42(m,8H),1.75-1.90(m,8H),1.93(s,6H),2.28(s,6H),2.70(m,2H),4.60(s,2H),7.13(s,2H)ppm。13C NMR(CDCl3):15.2,16.1,26.4,27.3,34.2,34.1,40.0,120.4,121.5,128.5,132.6,138.3,149.5ppm。
实施例14
3,3’-二-异丙基-4,4’,5,5’,6,6’-六甲基-2,2’-联苯酚的制备
在氮气下将3,4,5-三甲基酚(5g,37mmol)溶于30ml四氯化碳。在所述混合物中加入三氟甲磺酸钪(0.9g)和甲磺酸异丙酯(6.1g)。将所得混合物在氮气下加热回流3.5小时。然后将混合物倒入水中,分离各层。所得有机层用饱和碳酸氢钠洗涤,硫酸镁干燥、浓缩、用快速硅胶柱色谱纯化(用3%乙酸乙酯/己烷洗脱),得到3g 2-异丙基-3,4,5-三甲基酚(46%)。1H NMR(CDCl3):6.33(1H,s),4.47(1H,s),3.36(1H,quintet,J=12Hz),2.25(3H,s),2.18(1H,s),2.10(1H,s),1.35(6H,d,J=12Hz)。
将2-异丙基-3,4,5-三甲基酚(6g,34mmol)溶于10ml二氯甲烷,加入0.4g Cu(OH)Cl-TMEDA。在环境空气下搅拌所得混合溶液3小时。然后再加入0.4g Cu(OH)Cl-TMEDA,将所得混合溶液搅拌3小时。在所得黑色反应混合物中加入10%HCl溶液。将各层分离,将有机层浓缩,硫酸镁干燥,将所得残余物在硅胶上色谱分离,用5%乙醚/己烷洗脱,得到3.1g(52%)白色固体产物。1H NMR(CDCl3):4.74(1H,s),3.37(1H,quintet,J=7Hz),2.20(s,3H),2.08(s,3H),1.76(s,3H),1.26(d,6H,J=7Hz)。
实施例15
3,3’-二异丙基-5,5’,6,6’-四甲基-2,2’-联苯酚的制备
将装有机械搅拌器、空气输送插管、冷凝器,接收器的2升树脂罐放置在油浴中,加入610g 4-甲基百里酚(纯度99%,气相色谱法)。加入CuCl(3.05g)及N,N,N’,N’-四甲基乙二胺(7.14g),将所得混合物加热至100℃。经过插管输送的空气流速为1,000cc/分钟。3.5小时后,所述偶合反应基本完成,收集所得混合物。气相色谱显示混合物含90%3,3’-二异丙基-5,5’,6,6’-四甲基-2,2’-联苯酚、4%未反应单体和6%副产物。
实施例16
5,5’-二-t-丁基-3,3’-二-异丙基-6,6’-二甲基-2,2’-联苯酚的制备
将装有机械搅拌器、空气输送插管、冷凝器、接收器的500ml树脂罐放置在油浴中,加入4-t-丁基百里酚(99%纯度,气相色谱法)。加入CuCl(1.00g)、N,N,N’,N’-四甲基乙二胺(2.35g),将所得混合物加热至100℃。经过插管输送空气的流速为200cc/分钟。4小时后,收集所得混合物。气相色谱分析显示混合物含78%5,5’-二-t-丁基-3,3’-二-异丙基-6,6’-二甲基-2,2’-联苯酚、11%未反应单体及12%副产物。
实施例17
3,3’,5,5’-四异丙基-6,6’二甲基-2,2’-联苯酚的制备
在配有机械搅拌器、空气输送插管、冷凝器、接收器和电加热套的22升树脂罐中加入7.2kg4-异丙基百里酚(99%纯度气相色谱法)。加入CuCl(36.5g)和N,N,N’,N’-四甲基乙二胺(85.5g),将所得混合物加热至100℃。经过插管输送的空气流速为5升/分钟。11小时后,停止送气,冷却混合物以便收集。气相色谱分析显示混合物由74%3,3’,5,5’-四异丙基-6,6’二甲基-2,2’-联苯酚、8%未反应单体和18%副产物组成。
Claims (4)
1.一种制备下式化合物的方法:
该方法包括:在5℃-100℃范围的某一温度下,在非质子溶剂中,在含氧分子的气体和含铜催化剂存在下,氧化偶合下式化合物,
所述溶剂对所要偶合的化合物是惰性的,并且其闪点高于反应温度,所述含铜催化剂用包括以下步骤的方法制得:使铜卤盐与有机二胺化合物接触,
其中:
R1为C1-C6伯、仲或环烷基;
R2为氢、C1-C6伯、仲、叔或环烷基;
R3为C1-C6伯、仲、叔或环烷基;以及
R4为氢、C1-C6伯、仲或环烷基,
前提条件是R2和R4不同时为氢。
2.权利要求1的方法,其中所述铜卤盐为CuCl、CuBr、CuI或CuCl2。
3.权利要求2的方法,其中所述有机二胺化合物为以下化合物:
N,N,N’,N’-四乙基乙二胺、N,N,N’,N’-四乙基-1,3-丙二胺、N,N,N’,N’-四乙基甲二胺、N,N,N’,N’-四甲基-1,6-己二胺、N,N,N’,N’-四甲基-1,3-丙二胺、二哌啶子基甲烷、N,N,N’,N′-四甲基乙二胺或1,4-二氮杂双环-(2,2,2)-辛烷。
4.权利要求3的方法,其中R2、R3和R4各自为甲基或乙基。
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KR20140036307A (ko) | 2011-06-10 | 2014-03-25 | 인비스타 테크놀러지스 에스.에이.알.엘. | 니켈 금속-리간드 촉매 형성에서의 향상 |
JP2014523481A (ja) | 2011-06-10 | 2014-09-11 | インヴィスタ テクノロジーズ エスアエルエル | 流動床反応器を含む焼成プロセス及び還元プロセス |
CN102701964B (zh) * | 2012-05-09 | 2014-01-01 | 江西师范大学 | 合成4,4’-联苯二甲酸的方法 |
CN110292950A (zh) * | 2018-03-23 | 2019-10-01 | 和德化学(苏州)有限公司 | 铜-四乙基乙二胺、用其作为催化剂的克酮酸的制备方法 |
CN111909003B (zh) * | 2020-02-10 | 2023-05-30 | 广东欧凯新材料有限公司 | 一种制备公斤级新型联苯四酚的氧化偶联方法及其催化剂 |
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US4085124A (en) * | 1975-11-24 | 1978-04-18 | Ici Americas Inc. | Oxidative coupling of alkylphenols, alkoxyphenols and 1-naphthols catalyzed by metal complexes of amino compounds |
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US4132722A (en) | 1976-11-26 | 1979-01-02 | Ici Americas Inc. | Oxidative coupling of alkylphenols catalyzed by metal complexes of diimino acid |
US4139544A (en) | 1976-11-26 | 1979-02-13 | Ici Americas Inc. | Oxidative coupling of alkylphenols catalyzed by metal complexes of polyimino acids |
US4108908A (en) | 1977-02-18 | 1978-08-22 | Ici Americas Inc. | Oxidative coupling of alkylphenols or 1-naphthols catalyzed by metal complexes of thio-acid compounds |
US4354048A (en) | 1981-05-22 | 1982-10-12 | The Dow Chemical Company | Copper chromite catalysts for oxidative coupling of phenols |
JPH0742240B2 (ja) * | 1985-09-30 | 1995-05-10 | 三井石油化学工業株式会社 | ビフエノ−ル類の製造方法 |
US4880775A (en) | 1989-02-01 | 1989-11-14 | Basf K&F Corporation | Poly-alkylated benzodioxin musk compositions |
TW213465B (zh) | 1991-06-11 | 1993-09-21 | Mitsubishi Chemicals Co Ltd | |
EP0730574B1 (en) | 1993-11-23 | 1998-08-19 | E.I. Du Pont De Nemours And Company | Processes and catalyst compositions for hydrocyanation of monoolefins |
US5512695A (en) | 1994-04-14 | 1996-04-30 | E. I. Du Pont De Nemours And Company | Bidentate phosphite and nickel catalyst compositions for hydrocyanation of monoolefins |
US5512696A (en) | 1995-07-21 | 1996-04-30 | E. I. Du Pont De Nemours And Company | Hydrocyanation process and multidentate phosphite and nickel catalyst composition therefor |
US6031120A (en) | 1997-07-29 | 2000-02-29 | E. I. Du Pont De Nemours And Company | Selective synthesis of organodiphosphite compounds |
US6077979A (en) | 1999-02-18 | 2000-06-20 | E. I. Du Pont De Nemours And Company | Manufacture of 3,3',5,5'-tetramethyl-2,2'-biphenol |
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EP2279993A1 (en) | 2011-02-02 |
EP1467958B1 (en) | 2014-01-08 |
KR20040055819A (ko) | 2004-06-29 |
MXPA04004940A (es) | 2004-08-11 |
KR100880787B1 (ko) | 2009-02-02 |
US20030100802A1 (en) | 2003-05-29 |
JP2005510550A (ja) | 2005-04-21 |
BR0215097A (pt) | 2004-11-16 |
TW593251B (en) | 2004-06-21 |
PL371122A1 (en) | 2005-06-13 |
AU2002365394A1 (en) | 2003-06-10 |
CA2468104A1 (en) | 2003-06-05 |
CN1615287A (zh) | 2005-05-11 |
ES2449040T3 (es) | 2014-03-18 |
CN1982272A (zh) | 2007-06-20 |
EP1467958A1 (en) | 2004-10-20 |
WO2003045883A1 (en) | 2003-06-05 |
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