CN107522643A - 一类以二苯乙烯为共轭体系的硫鎓盐衍生物的制备新方法 - Google Patents
一类以二苯乙烯为共轭体系的硫鎓盐衍生物的制备新方法 Download PDFInfo
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- CN107522643A CN107522643A CN201710745964.2A CN201710745964A CN107522643A CN 107522643 A CN107522643 A CN 107522643A CN 201710745964 A CN201710745964 A CN 201710745964A CN 107522643 A CN107522643 A CN 107522643A
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- Prior art keywords
- sulfosalt
- talan
- reaction
- organic phosphine
- novel preparation
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- Pending
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- HDWLUGYOLUHEMN-UHFFFAOYSA-N Dinobuton Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1OC(=O)OC(C)C HDWLUGYOLUHEMN-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 241000425573 Talanes Species 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- -1 benzyl halogen Chemical class 0.000 claims abstract description 38
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 26
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 25
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000006467 substitution reaction Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000003839 salts Chemical group 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 3
- 150000002148 esters Chemical class 0.000 claims abstract 2
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical group CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- SSVFMICWXDVRQN-UHFFFAOYSA-N ethanol;sodium Chemical compound [Na].CCO SSVFMICWXDVRQN-UHFFFAOYSA-N 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- YGJORYBAYKUDBH-UHFFFAOYSA-N ethene;n-phenylaniline Chemical class C=C.C=1C=CC=CC=1NC1=CC=CC=C1 YGJORYBAYKUDBH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 54
- 239000000047 product Substances 0.000 description 21
- 238000004587 chromatography analysis Methods 0.000 description 15
- 238000001514 detection method Methods 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical class CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 235000002639 sodium chloride Nutrition 0.000 description 9
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical compound C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
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- 238000001291 vacuum drying Methods 0.000 description 7
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- 239000012153 distilled water Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- HZQLUIZFUXNFHK-UHFFFAOYSA-N 1-(bromomethyl)-4-phenylbenzene Chemical class C1=CC(CBr)=CC=C1C1=CC=CC=C1 HZQLUIZFUXNFHK-UHFFFAOYSA-N 0.000 description 2
- NAEZWYYYMVTEIV-UHFFFAOYSA-N 4-benzylsulfanylbenzaldehyde Chemical class C1=CC(C=O)=CC=C1SCC1=CC=CC=C1 NAEZWYYYMVTEIV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- RYZCGQUXJPHSSF-UHFFFAOYSA-N ethenylsulfanylmethylbenzene Chemical compound C=CSCC1=CC=CC=C1 RYZCGQUXJPHSSF-UHFFFAOYSA-N 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- VWDQHYQEQATEJN-UHFFFAOYSA-N 1,1'-biphenyl;ethene Chemical compound C=C.C1=CC=CC=C1C1=CC=CC=C1 VWDQHYQEQATEJN-UHFFFAOYSA-N 0.000 description 1
- MOHYOXXOKFQHDC-UHFFFAOYSA-N 1-(chloromethyl)-4-methoxybenzene Chemical compound COC1=CC=C(CCl)C=C1 MOHYOXXOKFQHDC-UHFFFAOYSA-N 0.000 description 1
- GTLWADFFABIGAE-UHFFFAOYSA-N 1-chloroethylbenzene Chemical compound CC(Cl)C1=CC=CC=C1 GTLWADFFABIGAE-UHFFFAOYSA-N 0.000 description 1
- XJNCVVVHUWTVCB-UHFFFAOYSA-N 3-methylsulfanylbenzaldehyde Chemical compound CSC1=CC=CC(C=O)=C1 XJNCVVVHUWTVCB-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical class FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KNHDDQIVHCDQIP-UHFFFAOYSA-N C(C1=CC=CC=C1)Br.[Cl] Chemical compound C(C1=CC=CC=C1)Br.[Cl] KNHDDQIVHCDQIP-UHFFFAOYSA-N 0.000 description 1
- SZBDPFSGPFVGSO-UHFFFAOYSA-N C(C1=CC=CC=C1)BrBr Chemical compound C(C1=CC=CC=C1)BrBr SZBDPFSGPFVGSO-UHFFFAOYSA-N 0.000 description 1
- UHTRFVWIJPKUML-UHFFFAOYSA-N C1(=CC=CC=C1)N(C1=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)N(C1=CC=CC=C1)[P]C1=CC=CC=C1 UHTRFVWIJPKUML-UHFFFAOYSA-N 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 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 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 1
- LKMCJXXOBRCATQ-UHFFFAOYSA-N benzylsulfanylbenzene Chemical compound C=1C=CC=CC=1CSC1=CC=CC=C1 LKMCJXXOBRCATQ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002027 dichloromethane extract Substances 0.000 description 1
- GDWXALVJBAAUJN-UHFFFAOYSA-N diethyl 4-methoxyphenyl phosphate Chemical class CCOP(=O)(OCC)OC1=CC=C(OC)C=C1 GDWXALVJBAAUJN-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
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- 239000003208 petroleum Substances 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical class BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- WCGIGOVLOFXAMG-UHFFFAOYSA-N silver;trifluoromethanesulfonic acid Chemical compound [Ag].OS(=O)(=O)C(F)(F)F WCGIGOVLOFXAMG-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
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- 150000003613 toluenes Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
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Abstract
本发明提供了一类以二苯乙烯为共轭体系的硫鎓盐衍生物的制备新方法,包括步骤,首先将不同基团取代的苄卤(Hal代表卤素原子)经与有机膦反应后,再与不同巯基取代的苯甲醛在碱性的条件下反应制备高产率的(I)‑a所示的取代二苯乙烯中间体,最后,将(I)‑a所示的中间体在银盐和卤代烷,或银盐和烷基酸酯的作用下,生成最终的硫鎓盐;当需要置换不同的阴离子时,采用盐交换方法实现。作为举例而非限定,本发明提供的方案,其有益效果在于:无需采用贵金属催化剂,原料易得,且成本不高;反应在室温下进行,操作简单,提纯方便;为工业化大规模生产以二苯乙烯为主体的硫鎓盐类衍生物提供了有利条件。
Description
技术领域
本发明涉及一类可以利用LED为激发光源,可以用于光刻以及光引发剂阳离子聚合,双光子微构筑等方面的具有较大共轭体系的硫鎓盐型衍生物的制备方法,尤其涉及一类以取代二苯乙烯为主体共轭体系的硫鎓盐衍生物的制备方法。
背景技术
硫鎓盐类化合物是一类重要的精细有机化学品材料;在以紫外光(UV)或可见光或LED(即Light-Emitting Diode)为光源的辐射固化技术领域,在光刻胶等半导体领域,其可在光辐照条件下产生强酸,特别是在阳离子光固化领域作为光引发剂有广泛的应用。光引发剂对光固化速率起着决定性作用。阳离子光聚合因为其固化过程体积收缩率小,光引发单体反应较于自由基聚合不被氧气阻聚,并且适用于厚膜光固化和对基材有较强的附着力,在涂料、油墨、胶粘剂和树脂基复合材料等领域有十分广阔的应用前景。
另一方面,光固化光源通常使用汞灯,汞蒸汽不符合世界节能环保产业发展的战略新趋势,因而在近年来LED光源获得了日益广泛的重视和快速的发展,且 LED光固化技术的应用大幅度降低了能源消耗和臭氧生成,产业持续增长动力强劲。对于LED体系固化,也需要既针对LED长波发射波长(365-420纳米,特别是 385-405纳米)有灵敏吸收的光引发剂。经研究发现,含有推拉电子结构的二苯乙烯共轭的硫鎓盐光生酸剂具有较好的吸收波长范围和优异的各项光化学物理性质以及良好的引发光聚合的能力。发明人已经报导了以二苯乙烯基团为共轭结构的硫鎓盐光生酸剂分子的制备方法及其性能(CN101943862A,CN101930174A,Xia R, et al.J.Chem.Mater.,2011,24:237),其基本结构如分子结构(a)和(b) 所示。
这些硫鎓盐结构体现出优良的光生酸性质,且其吸收波长处于350-425nm区间,可以利用新型的LED光源来激发。然而,对于报导的这类分子的制备过程,首先是利用Wittig反应制备取代苯乙烯,然后通过Pd催化的反应制备二苯乙烯共轭体系,最后用Ag盐与取代苄溴(氯)反应制备硫鎓盐。这些反应中苯乙烯的制备以及Pd催化的Heck反应均涉及到昂贵的原材料,且反应步骤较长。因此,能否设计出更简便、廉价的方法来制备出具有相同功能的分子结构、且能利用 LED光源激发的新型光生酸剂分子是业界的一大挑战。
发明内容
本发明的目的在于:克服现有技术的不足,提供一种工艺合理,操作简单,生产安全,且合成成本较低,适合工业化大规模生产的以二苯乙烯共轭结构为主体的硫鎓盐类衍生物的制备方法。
为实现上述目标,本发明提供了如下技术方案:
一种式(I)所示的以二苯乙烯为主体的硫鎓盐类衍生物的制备方法,首先,将取代的苄卤经与亚磷酸三乙酯等有机膦反应后;再和邻位、间位或对位甲巯基取代的苯甲醛,或者是邻位、间位或对位苄基巯基取代的苯甲醛在碱性(base) 条件下反应,即可制备出高产率的(I)-a结构;最后,(I)-a在银盐和卤代烷,或银盐和烷基酸酯的作用下生成目标产物硫鎓盐;当需要置换对应的阴离子时,则采用简单的盐交换方法即可实现。
在上述通式(I)化合物结构中:
R0为氢,卤素原子,R,OR,NRR’,CH2OH,CH2OR,或CH2NRR’;其中,R或R’彼此独立的是含有1-24个碳原子(标记为-C1-C24,下同)的直链或支链的烷基或-C6-C12芳基;R或R’结构中可以含有1-6个非连续的氧,氮,或硫元素;R和 R’同时存在时,其间也可以形成一个3-6元的环系结构。优选的,R0=Me;OMe; OCH2CH3;O(CH2)5CH3;N(CH3)2;N(CH2CH3)2;N(C6H5)2;N(4-MePh)2;N(CH2)4;N(CH2)5。
R1和R2彼此独立的是氢,是含有R3,R4,R5,R6,R7或R8,R9,R10,R11,R12取代的芳基(如图式所示,进而组成甲基或者不同取代苄基的硫鎓盐结构);其中, R3,R4,R5,R6,R7或R8,R9,R10,R11,R12彼此独立的是氢,卤素原子,R,OR,NRR’, CH2OH,CH2OR,或CH2NRR’;其中,R或R’彼此独立的是含有1-24个碳原子(标记为-C1-C24,下同)的直链或支链的烷基或-C6-C12芳基;R或R’结构中可以含有 1-6个非连续的氧,氮,或硫元素;R和R’同时存在时,其间也可以形成一个3-6 元的环系结构。优选的,R1=R2=H,即双甲基,或R1=H,R2=Ph或R1=H,R2=Ph,R8=R9= R11=R12=H,R10=CN,或R1=H,R2=Ph,R8=R9=R11=R12=H,R10=F,或R1=H,R2=Ph,R8=R9= R10=R11=R12=F,或R1=R2=Ph,R3=R4=R5=R6=R7=R8=R9=R10=R11=R12=H,或R1=R2=Ph, R3=R4=R6=R7=R8=R9=R10=R11=R12=H,R5=CN,或R1=R2=Ph,R3=R4=R5=R6=R7=H,R8=R9= R10=R11=R12=F;
硫鎓盐的取代位置是邻、间或对位;优选的,间位和对位。
Y和Z是对应的阴离子;优选的,可以是SO4 2-;CF3SO3 -;BF4 -;PF6 -;SbF6 -; B(Ph)4 -;B(pentafluorophenyl)-;C(CF3SO2)3 -;Al(OC(CF3)3)4。
所述的制备方法中,有机膦是三烷基、烷氧基或者芳基取代有机膦化合物;优选的,为亚磷酸三乙酯;三丁基膦,三苯基膦等。具体制备过程通过加热回流后产物减压蒸馏或重结晶即可提纯。
所述的制备方法中,(I)-a所示的二苯乙烯主体共轭结构是有机膦产物与取代醛在甲醇等常规溶剂、常温下搅拌制备出的,且产物的收集只需要过滤,洗涤即可,并能够获得高纯度的产物。碱(Base)优选为甲醇钠,乙醇钠,叔丁醇钾, NaH等。
所述的制备方法中,采用的均为可工业化生产的成本较低的原料,以降低反应成本。
所述的制备方法中,没有使用重金属催化剂等化合物,生产安全,保护环境。
本发明采用的以上技术方案,与现有技术相比,作为举例而非限定,具有以下的有益效果:本发明以容易制备的苄卤与有机膦反应产物为原料,在碱性条件下与邻位、间位或对位甲巯基取代的苯甲醛,或者是邻位、间位或对位苄基巯基取代的苯甲醛反应得到的硫醚前体为固体,反应在室温下进行,操作简单,提纯方便,并且原料来源广泛,成本均不高,适合工业化大规模生产,为工业化生产以二苯乙烯为主体的硫鎓盐类衍生物提供了有利条件。
具体实施方式
下面将结合具体实施例对本发明提供的一类以二苯乙烯为共轭体系的硫鎓盐 衍生物的制备新方法作进一步说明。结合下面说明,本发明的优点和特征将更加 清楚。
需要说明的是,本发明的实施例有较佳的实施性,并非是对本发明任何形式 的限定。本发明实施例中描述的技术特征或者技术特征的组合不应当被认为是孤 立的,它们可以被相互组合从而达到更好的技术效果。本发明优选实施方式的范 围也可以包括另外的实现,且这应被本发明实施例所属技术领域的技术人员所理 解。
对于相关领域普通技术人员已知的技术、方法和设备可能不作详细讨论,但 在适当情况下,所述技术、方法和设备应当被视为授权说明书的一部分。在这里 示出和讨论的所有示例中,任何具体值应被解释为仅仅是示例性的,而不是作为 限定。因此,示例性实施例的其它示例可以具有不同的值。
实施例一:按照如下路线合成出含有甲氧基的目标硫鎓盐分子
(a):K2CO3,DMF,100℃,4h;
(b):回流,4h;
(c):NaH,DMF,室温,12h;
(d):三氟甲烷磺酸甲酯(或者硫酸二甲酯);六氟锑酸钠,二氯甲烷,室温, 24h。
1.合成4-苄基巯基苯甲醛
在250mL三口烧瓶中加入K2CO3(20.37g,0.15mol)和75mL DMF,对体系抽真空充N2三次后置于100℃油浴中,分别依次注入4-氟苯甲醛(12.20g,0.1mol)和苄硫醇(12.40g,0.1mol),搅拌反应4h。将体系慢慢加入搅拌的10倍体积的蒸馏水中,过滤收集沉淀,40℃真空烘箱保存。产率91.0%。
1H NMR(400MHz,CDCl3)δ:9.91(s,1H),7.74(d,2H),7.41–7.27(m,7H), 4.24(s,2H)。
2.合成4-(4-甲氧基苯基)乙烯基苯基苄基硫醚
取对甲氧基苄氯与稍过量的亚磷酸三乙酯回流反应12小时后,反应混合物直接用于下一步反应。取(2.76g,12mmol)混合物于三口烧瓶中,室温下加入 NaH(1.20g,50mmol)和30mL DMF后,有气体产生,搅拌1小时候加入4-苄基巯基苯甲醛(2.28g,10mmol),室温搅拌反应2h后,经薄板层析检测反应结束,将体系倒入10倍体积的蒸馏水中,过滤收集沉淀,并用乙醇重结晶收集固体,40℃真空烘箱保存,产率78.0%。
3.合成目标硫鎓盐光生酸剂分子
在100mL的圆底烧瓶中分别加入三氟甲烷磺酸甲酯或者硫酸二甲酯 (7.5mmol),4-(4-甲氧基苯基)乙烯基苯基苄基硫醚(1.78g,5mmol)和20mL二氯甲烷。室温避光搅拌24小时,薄板层析检测反应结束。减压蒸馏浓缩滤液,用乙醚沉淀制备出三氟甲烷磺酸根或者硫酸根型的硫鎓盐产物。总产率68.5%或者36.8%。
盐交换制备六氟锑酸盐的方法是溶于最少量的丙酮中,滴入含有等当量的六氟锑酸水溶液中,抽滤析出的沉淀即为目标产物,该过程可以进行三遍以提高纯度。
HRMS for C23H23OS+:347.1465(calculated),347.1488(experimental)。
实施例二:按照如下路线合成出含有N,N-二苯基氨基的目标硫鎓盐分子
(a):甲苯,回流,24h;
(c):叔丁醇钾,THF,室温,12h;
(d):三氟甲烷磺酸甲酯,二氯甲烷,室温,24h。
1.合成磷盐
取一个干燥的250mL的圆底烧瓶,向其中加入4-N,N-二甲基氨基苄溴3.38g(10mmol,1equ),和30mL无水甲苯,再向反应体系内加入2.02g(10mmol,1equ) 三正丁基膦。反应回流24h。反应结束后,将反应烧瓶提起冷却至室温。再将烧瓶放入冰箱中冷冻2h。冷冻后烧瓶中出现白色固体,在低温下抽滤,用甲苯洗2次,得到白色粉末状产物4.84g,产率70%。
1H NMR(400MHz,CDCl3)δ:7.41-7.31(m,6H,PhH),7.01(d,J=8.3Hz,2H, PhH),6.91(d,J=8.7Hz,4H,PhH),4.21(d,J=14.8Hz,2H,CH2),2.44(m,6H,CH2), 1.48(s,12H,CH2),0.94(t,J=6.7Hz,9H,CH3)。
13C NMR(101MHz,CDCl3)δ:147.05,145.87,132.53,131.28,125.87, 116.30,26.54,24.02,23.87,23.72,18.97,18.50,13.48。
2.合成硫鎓盐前体4-N,N-二苯基氨基-3’-甲巯基二苯乙烯
取一个干燥的250mL圆底烧瓶中加入上一步合成产物2.62g(3.76mmol,1equ),加入无水四氢呋喃20mL,再加入3-(甲硫基)苯甲醛0.69g(4.51mmol, 1.2equ)。室温搅拌下加入叔丁醇钾固体0.51g(4.51mmol,1.2equ),反应室温搅拌18h。反应结束后,在一个大烧杯中配置饱和食盐水,将反应溶液倒入大烧杯中搅拌15min,用二氯甲烷萃取(3×3次)。将溶剂旋蒸,并抽真空。得到粘稠状黄色液体。经柱层析分离(二氯甲烷:石油醚=1:10v/v)得到淡黄色粉末状固体1.07g。产率51.7%。
1H NMR(400MHz,DMSO)δ:7.54(d,J=8.6Hz,2H,PhH),7.47(d,J=8.7Hz, 4H,PhH),7.43(s,1H,PhH),7.35(d,J=7.7Hz,1H,PhH),7.29(t,J=7.7Hz, 1H,CH=CH),7.23(d,J=16.4Hz,1H,CH=CH),7.15-7.08(m,2H,PhH),6.97 (dd,J=12.1,8.7Hz,6H,PhH),2.48(s,3H,CH3)。
13C NMR(101MHz,CDCl3)δ:146.45,146.24,138.92,138.00,132.47, 132.41,129.13,128.47,127.70,127.21,125.74,125.50,124.55,124.12, 123.23,115.88,15.92。
3.合成硫鎓盐
取100mL干燥的圆底烧瓶,加入上一步合成的前体300mg(0.54mmol,1equ),溶于20mL干燥的二氯甲烷中,用铝箔将圆底烧瓶全部包住避光。将圆底烧瓶放入低温浴槽中冷却至0℃,用微量注射器注入三氟甲烷磺酸甲酯0.07mL(0.106g, 0.65mmol,1.2equiv),搅拌15min后,在室温下搅拌反应24h。反应结束后减压蒸馏浓缩滤液,用乙醚沉淀得到目标产物。产率70.1%。
1H NMR(400MHz,CD3CN)δ:8.03(s,1H,PhH),7.88(d,J=7.8Hz,1H,PhH), 7.74(d,J=8.4Hz,1H,PhH),7.67(t,J=7.8Hz,1H,PhH),7.50(d,J=8.6Hz, 2H,PhH),7.41(d,J=8.78Hz,4H,PhH),7.34(d,J=16.4Hz,1H,CH=CH),7.14 (d,J=16.3Hz,1H,CH=CH),7.02(d,J=8.6Hz,2H,PhH),6.96(d,J=8.79Hz, 4H,PhH),3.16(s,6H,CH3)。
13C NMR(101MHz,CD3CN)δ:146.77,145.91,140.37,132.11,131.61, 131.16,131.01,130.82,127.76,127.50,126.42,125.74,125.39,124.21, 123.40,117.01,115.26,27.98。
实施例三:按照如下路线合成出含有甲基的目标硫鎓盐分子
(a):K2CO3,DMF,100℃,4h;
(b):回流,4h;
(c):NaH,DMF,室温,12h;
(d):三氟甲烷磺酸甲酯(或者硫酸二甲酯),六氟磷酸钾,二氯甲烷,室温, 24h。
1.合成4-苄基巯基苯甲醛
步骤同示例一中合成过程。
1H NMR(400MHz,CDCl3)δ:9.91(s,1H),7.74(d,2H),7.41-7.27(m,7H), 4.24(s,2H)。
2.合成4-(4-甲基苯基)乙烯基苯基苄基硫醚
取对甲基苄氯与过量的亚磷酸三乙酯反应产物(2.91g,12mmol)于三口烧瓶中,室温下加入NaH(1.23g,50mmol)和100mL DMF后,发现有气体产生,而后加入4-苄基巯基苯甲醛(2.25g,10mmol),室温搅拌反应12h后,经薄板层析检测反应结束,将体系倒入10倍体积的蒸馏水中,过滤收集沉淀,并用乙醇重结晶收集固体,40℃真空烘箱保存,产率64.4%。
HRMS(M+H)for C22H21S:317.1319(calculated),317.1362(experimental); (M+Na)for C22H20NaS:339.1183(calculated),339.1172(experimental)。
3.合成目标硫鎓盐光生酸剂分子
在100mL的圆底烧瓶中分别加入三氟甲烷磺酸甲酯或者硫酸二甲酯(7.5mmol),4-(4-甲基苯基)乙烯基苯基苄基硫醚(1.57g,5mmol)和20mL二氯甲烷。室温避光搅拌24小时,薄板层析检测反应结束。减压蒸馏浓缩滤液,用纯的乙酸乙酯为展开剂过硅胶柱得到硫鎓盐粗产物。再进行盐交换两次,总产率37.2%。
HRMS for C23H23S+:331.1515(calculated),331.1527(experimental)。
实施例四:按照如下路线合成目标硫鎓盐分子
(a):回流,4h;
(b):NaH,DMF,室温,12h;
(c):三氟甲烷磺酸银,4-氰基苄溴,六氟磷酸钾,二氯甲烷,室温,24h。
1.合成4-甲氧基苯基磷酸二乙酯
在100mL三口烧瓶中分别称取4-甲氧基苄氯(1.56g,10mmol),亚磷酸三乙酯(8.30g,50mmol),升温至150℃冷凝回流,反应4h经薄板层析检测反应结束,真空干燥后可直接进行下一步反应,干燥后净重9.21g,内含产物4-甲氧基苯基磷酸二乙酯约2.58g。
2.合成4-(4-甲氧基苯基)乙烯基苯基甲基硫醚
取上述全部反应后产物(9.21g,10mmol)于三口烧瓶中,室温下加入 NaH(1.21g,50mmol)和100mL DMF后,发现有气体产生,而后加入4-甲基巯基苯甲醛(1.52g,10mmol),室温搅拌反应12h后,经薄板层析检测反应结束,将体系倒入10倍体积的蒸馏水中,过滤收集沉淀,并用乙醇重结晶收集固体,40℃真空烘箱保存,产率52.7%(1.35g)。
HRMS(M+H)for C16H17OS:257.0955(calculated),257.0945(experimental); (M+Na)for C16H16NaOS:279.0820(calculated),279.0831(experimental)。
3.合成目标硫鎓盐光生酸剂分子
在100mL的圆底烧瓶中分别加入避光烘干后的三氟甲烷磺酸银(1.93g,7.5mmol),抽真空充氮气后注入溶于10mL二氯甲烷的4-(4-甲氧基苯基)乙烯基苯基甲基硫醚(1.28g,5mmol)和溶于10mL二氯甲烷的4-氰基苄溴(1.96g, 10mmol)。室温避光搅拌24小时,薄板层析检测反应结束。减压蒸馏浓缩滤液,用纯的乙酸乙酯为展开剂过硅胶柱得到硫鎓盐粗产物。再用饱和的六氟磷酸钾溶液进行盐交换两次,总产率45.8%。
HRMS for C24H22NOS+:372.1417(calculated),372.1453(experimental)。
实施例五:按照如下路线合成出含有N,N-二苯氨基苯基的目标硫鎓盐分子
(a):硼氢化钠,二氯甲烷,无水乙醇,室温,2h;
(b):三溴化磷,无水乙醚,室温,15h;
(c):回流,4h;
(d):NaH,DMF,室温,12h;
(e):三氟甲烷磺酸甲酯,六氟磷酸钾,二氯甲烷,室温,24h。
1.合成N,N-二苯氨基苄溴
在干燥的250mL圆底烧瓶中加入N,N-二苯氨基苯甲醛(4.10g,15mmol),48mL 无水二氯甲烷,16mL无水乙醇,再加入硼氢化钠(0.57g,15mmol),室温搅拌反应 2小时。而后用二氯甲烷萃取,干燥后蒸干得到白色固体粉末状产物,产物3.92g,产率95.0%。
将上述产物(3.92g,14mmol)加入干燥的250mL圆底烧瓶,再加入27mL无水乙醚,氮气保护低温条件下用恒压滴液漏斗滴加加入0.81mL三溴化磷(2.27g, 8.4mmol)和6mL无水乙醚的混合溶液。滴加完成后,室温搅拌15小时,经薄板层析检测反应结束,将反应液倒入饱和碳酸钠冰水溶液中并搅拌15分钟,而后用二氯甲烷萃取,干燥,浓缩后得到产物N,N-二苯氨基苄溴4.10g,产率为87%。
2.合成N,N-二苯氨基苯基磷酸二乙酯
称取N,N-二苯氨基苄溴(3.38g,10mmol)和亚磷酸三乙酯(8.30g,50mmol) 加入干燥的250mL三口烧瓶中,升温至150℃冷凝回流,反应4h经薄板层析检测反应结束,真空干燥后可直接进行下一步反应,干燥后净重10.62g,经理论计算内含产物N,N-二苯氨基苯基磷酸二乙酯约3.95g。
3.合成4-(N,N-二苯氨基苯基)乙烯基苯基甲基硫醚
取上述全部反应后产物(10.62g,10mmol)于三口烧瓶中,室温下加入 NaH(1.22g,50mmol)和100mL DMF后,发现有气体产生,而后加入4-甲基巯基苯甲醛(1.53g,10mmol),室温搅拌反应12h后,经薄板层析检测反应结束,将体系倒入10倍体积的蒸馏水中,过滤收集沉淀,并用乙醇重结晶收集固体,40℃真空烘箱保存,产率49.3%(1.94g)。
4.合成目标硫鎓盐光生酸剂分子
在100mL的圆底烧瓶中分别加入三氟甲烷磺酸甲酯或者硫酸二甲酯 (7.5mmol),4-(N,N-二苯氨基苯基)乙烯基苯基甲基硫醚(1.94g,5mmol)和20mL 二氯甲烷。室温避光搅拌24小时,薄板层析检测反应结束。减压蒸馏浓缩滤液,用纯的乙酸乙酯为展开剂过硅胶柱得到硫鎓盐粗产物。再进行盐交换两次,总产率43.1%。
HRMS for C28H26NS+:408.1781(calculated),408.1749(experimental)。
实施例六:按照如下路线合成出含有联苯的目标硫鎓盐分子
(a):无水碳酸钾,四(三苯基膦)钯,甲苯,无水乙醇,去离子水,100℃;
(b):回流,4h;
(c):NaH,DMF,室温,12h;
(d):硫酸二甲酯,六氟磷酸钾,二氯甲烷,室温,24h。
1.合成4-苯基苄溴
在干燥的250mL三口烧瓶中加入苯硼酸(2.44g,0.02mol),对溴苄溴(4.99g,0.02mol),四(三苯基膦)钯(0.23g,0.2mmol),加入无水碳酸钾(8.28g,0.06mol),和50mL甲苯,30mL无水乙醇,10mL去离子水再加入硼氢化钠(0.57g,15mmol),油浴加热至100℃,经薄板层析检测反应结束后,用乙酸乙酯和正己烷体系进行硅胶柱层析,收集产物,4.07g,产率82.4%。
2.合成二(1,1-联苯)磷酸二乙酯
称取4-苯基苄溴(2.47g,0.01mol)和亚磷酸三乙酯(8.34g,0.05mol)加入干燥的250mL三口烧瓶中,升温至150℃冷凝回流,反应4h经薄板层析检测反应结束,真空干燥后可直接进行下一步反应,干燥后净重9.68g,经理论计算内含产物 N,N-二苯氨基苯基磷酸二乙酯约3.04g。
3.合成二(1,1-联苯)乙烯基苯基甲基硫醚
取上述全部反应后产物(9.68g,0.01mol)于三口烧瓶中,室温下加入 NaH(1.24g,0.05mol)和100mL DMF后,发现有气体产生,而后加入4-甲基巯基苯甲醛(1.52g,0.01mol),室温搅拌反应12h后,经薄板层析检测反应结束,将体系倒入10倍体积的蒸馏水中,过滤收集沉淀,并用乙醇重结晶收集固体,40℃真空烘箱保存,产率56.3%(1.70g)。
4.合成目标硫鎓盐光生酸剂分子
在100mL的圆底烧瓶中分别加入硫酸二甲酯(0.95g,7.5mmol),二(1,1-联苯)乙烯基苯基甲基硫醚(1.51g,5mmol)和20mL二氯甲烷。室温避光搅拌24小时,薄板层析检测反应结束。减压蒸馏浓缩滤液,用纯的乙酸乙酯为展开剂过硅胶柱得到硫鎓盐粗产物。再进行盐交换两次,总产率48.6%。
HRMS for C22H21S+:317.1359(calculated),317.1343(experimental)。
本发明的技术方案,作为举例而非限定,具有如下有益效果:本发明以容易制备的苄卤与有机膦反应产物为原料,在碱性条件下与邻位、间位或对位甲巯基取代的苯甲醛,或者是邻位、间位或对位苄基巯基取代的苯甲醛反应得到的硫醚前体为固体,反应在室温下进行,操作简单,提纯方便,并且原料来源广泛,成本均不高,适合工业化大规模生产,为工业化生产以二苯乙烯为主体的硫鎓盐类衍生物提供了有利条件。
上述描述仅是对本发明较佳实施例的描述,并非是对本发明范围的任何限定。任何熟悉该领域的普通技术人员根据上述揭示的技术内容做出的任何变更或修饰均应当视为等同的有效实施例,均属于本发明技术方案保护的范围。
Claims (4)
1.一类以二苯乙烯为共轭体系的硫鎓盐衍生物的制备新方法,其特征在于:该制备新方法为,先将取代苄卤与有机膦加热回流反应得到有机膦产物;再将有机膦产物与邻位、间位或对位甲巯基取代的苯甲醛,或者是邻位、间位或对位苄基巯基取代的苯甲醛在碱性条件下常温搅拌反应,并经过过滤、洗涤得到(I)-a所示的二苯乙烯中间体;最后,将(I)-a所示的二苯乙烯中间体在银盐和卤代烷,或银盐和烷基酸酯的作用下,生成(I)所示的目标产物硫鎓盐;需要置换对应的阴离子时,采用盐交换方法实现;
在上述通式(I)所示的化合物结构中,
R0为氢,卤素原子,R,OR,NRR’,CH2OH,CH2OR,或CH2NRR’,其中R或R’彼此独立的是含有1-24个碳原子(标记为-C1-C24,下同)的直链或支链的烷基或-C6-C12芳基,R或R’结构中可以含有1-6个非连续的氧,氮,或硫元素,R和R’同时存在时其间也可以形成一个3-6元的环系结构;
R1和R2彼此独立的是氢,是含有R3,R4,R5,R6,R7或R8,R9,R10,R11,R12取代的芳基,其中R3,R4,R5,R6,R7或R8,R9,R10,R11,R12彼此独立的是氢,卤素原子,R,OR,NRR’,CH2OH,CH2OR,或CH2NRR’,其中R或R’彼此独立的是含有1-24个碳原子(标记为-C1-C24,下同)的直链或支链的烷基或-C6-C12芳基,R或R’结构中可以含有1-6个非连续的氧,氮,或硫元素,R和R’同时存在时其间也可以形成一个3-6元的环系结构;
Y和Z是对应的阴离子。
2.根据权利要求1所述的制备新方法,其特征在于:步骤(A)中采用的有机膦为三烷基、烷氧基或芳基取代有机膦化合物。
3.根据权利要求2所述的制备新方法,其特征在于:所述有机膦为亚磷酸三乙酯、三丁基膦、或三苯基膦。
4.根据权利要求1所述的制备新方法,其特征在于:步骤(B)中采用的碱为甲醇钠、乙醇钠、叔丁醇钾或氢化纳。
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