CN106349291A - 一类dopo衍生物的制备方法 - Google Patents
一类dopo衍生物的制备方法 Download PDFInfo
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- CN106349291A CN106349291A CN201610601334.3A CN201610601334A CN106349291A CN 106349291 A CN106349291 A CN 106349291A CN 201610601334 A CN201610601334 A CN 201610601334A CN 106349291 A CN106349291 A CN 106349291A
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- 238000000034 method Methods 0.000 title abstract description 5
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical class C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 20
- 241001597008 Nomeidae Species 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 7
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 5
- -1 entrainer Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical group ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 3
- 229940005991 chloric acid Drugs 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- YJPVTCSBVRMESK-UHFFFAOYSA-L strontium bromide Chemical compound [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 claims description 3
- 229940074155 strontium bromide Drugs 0.000 claims description 3
- 229910001625 strontium bromide Inorganic materials 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical group CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 claims description 2
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 claims description 2
- BUZMJVBOGDBMGI-UHFFFAOYSA-N 1-phenylpropylbenzene Chemical compound C=1C=CC=CC=1C(CC)C1=CC=CC=C1 BUZMJVBOGDBMGI-UHFFFAOYSA-N 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 2
- 238000005654 Michaelis-Arbuzov synthesis reaction Methods 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012675 alcoholic extract Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229940097267 cobaltous chloride Drugs 0.000 claims description 2
- 229940079721 copper chloride Drugs 0.000 claims description 2
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- 229940046149 ferrous bromide Drugs 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- 229960002337 magnesium chloride Drugs 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical group CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 150000003009 phosphonic acids Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- UYAGPULHTNCMOT-UHFFFAOYSA-N [B].FB(F)F Chemical compound [B].FB(F)F UYAGPULHTNCMOT-UHFFFAOYSA-N 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- 239000011592 zinc chloride Substances 0.000 claims 1
- 235000005074 zinc chloride Nutrition 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 4
- 229940126062 Compound A Drugs 0.000 abstract 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 235000009518 sodium iodide Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
一类DOPO衍生物的制备方法，涉及化学材料领域的阻燃剂，化合物A和化合物B在催化剂、夹带剂、溶剂的存在下，在1‑6个大气压、150‑220℃下脱水反应4‑30h制得化合物I，其分子式为
Description
本申请为申请日为2013年07月05日、申请号为201310281334.6、名称为“一类DOPO衍生物的制备方法”的发明专利申请的分案申请。
技术领域
本发明涉及化学材料领域的阻燃剂，尤其涉及一类DOPO衍生物的制备方法。
背景技术
有机磷系阻燃剂因生烟量少，不易形成有毒气体和腐蚀性气体，具有环境友好性，因此被公认为可替代卤系阻燃剂的重要品种。在环氧树脂和板材领域，反应型的有机磷系阻燃剂，如DOPO衍生物，应用较为常见，它们通过共价键的方式连接到环氧树脂上面，对材料的性能本身影响较小。而作为添加型的有机磷系阻燃剂，在环氧树脂领域的应用则较为少见，因为它对阻燃剂的熔点和稳定性要求较高，一般的阻燃剂难以达到要求。
作为添加型的阻燃剂，以醚键连接的DOPO衍生物虽然有少量专利报道，如Japanese Kokai Patent Application NO.Hei 11[1999]-106619，但对其合成方法研究得较少，文献中是以DOPO与含卤素的化合物为原料进行反应，该制备方法产率低且成本高。
发明内容
本发明针对现有技术的不足，提供了一种简单、高效的一类DOPO衍生物(化合物I)的制备方法，本方法所得产品易于提纯，且收率高、成本低。
具体方案为：一类DOPO衍生物的制备方法，其特征在于化合物A和化合物B在催化剂、夹带剂、溶剂的存在下，在1-6个大气压、150-220℃下脱水反应4-30h制得化合物I；
化合物I的分子式为：
其中，R1,R2为氢、烷基、芳基或者杂环取代基(取代基上均不含能与醇羟基反应的位点)；m和n分别为2-8；
化合物A的分子式为：
其中，R1和R2的定义与上述相同；
化合物B的分子式为：
其中，m和n的定义与上述相同。
反应式为：
化合物B和化合物A的投料摩尔比优选为0.4到3。因为比例太低，则化合物A转换率难以提高；而比例过高，则单取代物增多，且面临着化合物B的回收问题。
本发明中，催化剂为适用于脱水反应或者Arbuzov反应的催化剂，包括烷基卤化物，碱金属卤化物，碱土金属卤化物，过渡金属卤化物或者酸催化剂。具体的包括碘化钠，溴化钠，碘化钾，溴化钾，氯化锂，溴化锂，碘化锂，C1-C6的烷基碘化物，C1-C6的烷基溴化物，氯化铁，溴化铁，氯化亚铁，溴化亚铁，氯化镁，氯化镍，溴化镍，氯化铝，氯化钛，氯化锡，氯化锌，铜粉，氯化铜，氯化钴，溴化锶，硫酸，盐酸，氯酸，高氯酸，磷酸，氢溴酸，氢氟酸，硝酸，草酸，烷基磺酸，芳基磺酸，三氟乙酸，三氟甲磺酸，膦酸，二乙基氯化铝，三氟化硼，酸性沸石，酸性粘土，聚合物磺酸的一种或组合。催化剂的用量为化合物A摩尔量的0.1-7％。
作为优选，溶剂为高沸点溶剂，也就是在常压下沸点大于150℃，熔点大于-100℃。具体包括二苯甲烷，二苯丙烷，二苯乙烷，联苯，二苯醚，十氢萘，四氢萘，二乙基苯，环己基苯，1,3-二异丙基苯，二甲亚砜，N,N-二甲基甲酰胺，二甲基乙酰胺，N-甲基吡咯烷酮，乙二醇二甲醚，乙二醇二乙醚，或者上述化合物的混合物。
作为优选，所用夹带剂为低沸点溶剂，即常压下其沸点小于150℃。具体包括苯，甲苯，二甲苯，二氯乙烷，吡啶，乙腈，氯仿，四氯化碳，戊烷，己烷，庚烷，辛烷，环己烷，甲基环己烷，乙基苯，或者它们的混合物。
化合物I的合成是通过化合物A的P-H键与化合物B的-OH两个活性位点之间进行反应，而化合物A上的取代基R1和R2不参与反应，同时化合物B中的烷氧基链也不参与反应，因此R1,R2以及m,n的变化对反应条件都没有太大影响。于是，选取化合物I-a为例来具体阐述本专利的制备方法。即：R1,R2＝H，化合物A为DOPO；m,n＝2，化合物B为二甘醇(DEG)。
反应式为：
具体实施方式
实施例1，DOPO衍生物化合物I-a的制备
向烧瓶中加入DOPO(21.6g,0.1mol)，DEG(8.49g,0.08mol)，碘化钠(0.2g)，二甲苯(10g)和二苯甲烷(40g),并装置好油水分离器和温度计，在氮气保护下，加热到195℃，8小时后停止反应，磷谱显示DOPO转换率为97％。冷却后加入20mL乙醇，在70℃搅拌半个小时，然后趁热过滤，收集固体，在真空干燥箱中于110℃下干燥12小时。产物纯度大于99％，收率为82％(收率以DOPO为标准计算，以下实施例均相同)。
实施例2，DOPO衍生物化合物I-a的制备
向烧瓶中加入DOPO(43.2g,0.20mol)，DEG(21.2g,0.20mol)，对甲苯磺酸(0.4g)，二甲苯(13g)和二苯甲烷(90g),并装置好油水分离器和温度计，在氮气保护下，加热到200℃，8小时后停止反应，磷谱显示DOPO转换率为96％。冷却后加入40mL乙醇，在70℃搅拌半个小时，然后趁热过滤，收集固体，在真空干燥箱中于110℃下干燥12小时。产物纯度大于99％，收率为81％。
实施例3，DOPO衍生物化合物I-a的制备
向烧瓶中加入DOPO(43.2g,0.20mol)，DEG(21.2g,0.20mol)，碘化钠(0.4g)，二甲苯(23g)和二苯甲烷(90g),并装置好油水分离器和温度计，在氮气保护下，加热到195℃，于3个大气压下反应4小时后停止反应，磷谱显示DOPO转换率为97％。冷却后加入40mL乙醇，在70℃搅拌半个小时，然后趁热过滤，收集固体，在真空干燥箱中于110℃下干燥12小时。产物纯度大于99％，收率为83％。
实施例4～20，参照实施例1～3，修改部分参数，如下表所示：
尽管本发明的内容已经通过上述优选实施例做了详细的介绍，但应当认识到上述的描述不应被认为是对本发明的限制。任何本领域的技术人员能思之的变化，都应落在本申请的保护范围内。
Claims (10)
1.一类DOPO衍生物的制备方法，其特征在于化合物A和化合物B在催化剂、夹带剂、溶剂的存在下，在1-6个大气压、150-220℃下脱水反应4-30h，所述的催化剂为适用于脱水反应或者Arbuzov反应的催化剂；
化合物A的分子式为：
R1,R2为杂环取代基(取代基上均不含能与醇羟基反应的位点)；
化合物B的分子式为：
m和n分别为2-8。
2.根据权利要求1所述的一类DOPO衍生物的制备方法，其特征在于化合物B和化合物A的投料摩尔比为0.4到3。
3.根据权利要求1所述的一类DOPO衍生物的制备方法，其特征在催化剂的用量为化合物A摩尔量的0.1-7％。
4.根据权利要求1所述的一类DOPO衍生物的制备方法，其特征在于催化剂具体包括碘化钠，溴化钠，碘化钾，溴化钾，氯化锂，溴化锂，碘化锂，C1-C6的烷基碘化物，C1-C6的烷基溴化物，氯化铁，溴化铁，氯化亚铁，溴化亚铁，氯化镁，氯化镍，溴化镍，氯化铝，氯化钛，氯化锡，氯化锌，铜粉，氯化铜，氯化钴，溴化锶，硫酸，盐酸，氯酸，高氯酸，磷酸，氢溴酸，氢氟酸，硝酸，草酸，烷基磺酸，芳基磺酸，三氟乙酸，三氟甲磺酸，膦酸，二乙基氯化铝，三氟化硼，酸性沸石，酸性粘土，聚合物磺酸的一种或组合。
5.根据权利要求1所述的一类DOPO衍生物的制备方法，其特征在于溶剂为高沸点溶剂，即在常压下沸点大于150℃，熔点大于-100℃。
6.根据权利要求5所述的一类DOPO衍生物的制备方法，其特征在于溶剂包括二苯甲烷，二苯丙烷，二苯乙烷，联苯，二苯醚，十氢萘，四氢萘，二乙基苯，环己基苯，1,3-二异丙基苯，二甲亚砜，N,N-二甲基甲酰胺，二甲基乙酰胺，N-甲基吡咯烷酮，乙二醇二甲醚，乙二醇二乙醚，或者上述化合物的混合物。
7.根据权利要求1所述的一类DOPO衍生物的制备方法，其特征在于夹带剂为低沸点溶剂，即常压下其沸点小于150℃。
8.根据权利要求7所述的一类DOPO衍生物的制备方法，其特征在于夹带剂包括苯，甲苯，二甲苯，二氯乙烷，吡啶，乙腈，氯仿，四氯化碳，戊烷，己烷，庚烷，辛烷，环己烷，甲基环己烷，乙基苯，或者它们的混合物。
9.根据权利要求8所述的一类DOPO衍生物的制备方法，其特征在于催化剂具体包括溴化钠，三氟乙酸，对甲苯磺酸，氯化镁，氯化钛，氯化铜，溴化锶，氯酸的一种或组合。
10.根据权利要求8所述的一类DOPO衍生物的制备方法，其特征在于溶剂包括二苯醚，二乙苯，四氢萘，N-甲基吡咯烷酮，或者上述化合物的混合物。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102971333A (zh) * | 2010-03-31 | 2013-03-13 | 雅宝公司 | 制备dopo衍生的化合物及其组合物的方法 |
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| CN102428091A (zh) * | 2009-05-19 | 2012-04-25 | 雅宝公司 | Dopo衍生的阻燃剂及环氧树脂组合物 |
| CN102971333A (zh) * | 2010-03-31 | 2013-03-13 | 雅宝公司 | 制备dopo衍生的化合物及其组合物的方法 |
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| CN108623634B (zh) * | 2018-07-11 | 2020-07-28 | 四川省乐山市华莱利科技有限公司 | 一种环状磷酸酯阻燃剂的制备方法 |
| CN109134543A (zh) * | 2018-10-17 | 2019-01-04 | 中南林业科技大学 | 一种含醚键dopo类似物的制备方法 |
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