CN102381947B - Synthesis method of chiral 2,2 '- di-alkoxy-1, 1'-binaphthyl - Google Patents
Synthesis method of chiral 2,2 '- di-alkoxy-1, 1'-binaphthyl Download PDFInfo
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- CN102381947B CN102381947B CN201110233332.0A CN201110233332A CN102381947B CN 102381947 B CN102381947 B CN 102381947B CN 201110233332 A CN201110233332 A CN 201110233332A CN 102381947 B CN102381947 B CN 102381947B
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- China
- Prior art keywords
- binol
- solvent
- dinaphthalene
- chirality
- dialkoxy
- 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 - Fee Related
Links
- 238000001308 synthesis method Methods 0.000 title abstract 3
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 claims abstract description 63
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000002904 solvent Substances 0.000 claims abstract description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 19
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 33
- 238000005660 chlorination reaction Methods 0.000 claims description 30
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 16
- 238000012986 modification Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229940043232 butyl acetate Drugs 0.000 claims description 12
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 12
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000010189 synthetic method Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 239000010410 layer Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 7
- 239000002798 polar solvent Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 6
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005194 fractionation Methods 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 230000009466 transformation Effects 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- 150000001350 alkyl halides Chemical class 0.000 claims description 4
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 4
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 claims description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000015320 potassium carbonate Nutrition 0.000 claims description 4
- 238000010025 steaming Methods 0.000 claims description 4
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 2
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 claims description 2
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 claims description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 2
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims description 2
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical compound CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-UHFFFAOYSA-N 0.000 claims description 2
- ZTEHOZMYMCEYRM-UHFFFAOYSA-N 1-chlorodecane Chemical compound CCCCCCCCCCCl ZTEHOZMYMCEYRM-UHFFFAOYSA-N 0.000 claims description 2
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 claims description 2
- DZMDPHNGKBEVRE-UHFFFAOYSA-N 1-chloroheptane Chemical compound CCCCCCCCl DZMDPHNGKBEVRE-UHFFFAOYSA-N 0.000 claims description 2
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 claims description 2
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 claims description 2
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 claims description 2
- ANOOTOPTCJRUPK-UHFFFAOYSA-N 1-iodohexane Chemical compound CCCCCCI ANOOTOPTCJRUPK-UHFFFAOYSA-N 0.000 claims description 2
- UWLHSHAHTBJTBA-UHFFFAOYSA-N 1-iodooctane Chemical compound CCCCCCCCI UWLHSHAHTBJTBA-UHFFFAOYSA-N 0.000 claims description 2
- BLXSFCHWMBESKV-UHFFFAOYSA-N 1-iodopentane Chemical compound CCCCCI BLXSFCHWMBESKV-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- BFQLXCMOMIFTCB-UHFFFAOYSA-N CC(C)C.[Br] Chemical compound CC(C)C.[Br] BFQLXCMOMIFTCB-UHFFFAOYSA-N 0.000 claims description 2
- JVRCTUOWLWHVMJ-UHFFFAOYSA-N CC(C)C.[I] Chemical compound CC(C)C.[I] JVRCTUOWLWHVMJ-UHFFFAOYSA-N 0.000 claims description 2
- FUKFNEMODDCPFZ-UHFFFAOYSA-N CC(C)CCC.[Cl] Chemical compound CC(C)CCC.[Cl] FUKFNEMODDCPFZ-UHFFFAOYSA-N 0.000 claims description 2
- FKAYSTCJTTUGHH-UHFFFAOYSA-N CC(CCC)C.[Br] Chemical compound CC(CCC)C.[Br] FKAYSTCJTTUGHH-UHFFFAOYSA-N 0.000 claims description 2
- KAEYRXKPNFTNBH-UHFFFAOYSA-N CCCCCCCCCCCCCC.[Cl] Chemical compound CCCCCCCCCCCCCC.[Cl] KAEYRXKPNFTNBH-UHFFFAOYSA-N 0.000 claims description 2
- DIXGRQMWKSYIBF-UHFFFAOYSA-N CCCCCCCCCCCCCCCC.[Br] Chemical compound CCCCCCCCCCCCCCCC.[Br] DIXGRQMWKSYIBF-UHFFFAOYSA-N 0.000 claims description 2
- BOXMCJRNMGUMDI-UHFFFAOYSA-N CCCCCCCCCCCCCCCC.[Cl] Chemical compound CCCCCCCCCCCCCCCC.[Cl] BOXMCJRNMGUMDI-UHFFFAOYSA-N 0.000 claims description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- ZHGVBKGHGOWFOG-UHFFFAOYSA-N [I].CCCCCCC Chemical compound [I].CCCCCCC ZHGVBKGHGOWFOG-UHFFFAOYSA-N 0.000 claims description 2
- QASKCGNZJHBTDJ-UHFFFAOYSA-N [SiH4].BrCCCCC Chemical compound [SiH4].BrCCCCC QASKCGNZJHBTDJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- -1 bromine isopropyl alkane Chemical class 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical group IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 2
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 238000006266 etherification reaction Methods 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 abstract 2
- GQVKRDRDFJTFEZ-UHFFFAOYSA-N 3-bromo-4,6-dimethyl-[1,2]thiazolo[5,4-b]pyridine Chemical compound CC1=CC(C)=C2C(Br)=NSC2=N1 GQVKRDRDFJTFEZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 2
- 229950011260 betanaphthol Drugs 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000006340 racemization Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 150000001348 alkyl chlorides Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- KMWHQYDMBYABKL-UHFFFAOYSA-N 1-iodohexadecane Chemical class CCCCCCCCCCCCCCCCI KMWHQYDMBYABKL-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KMPWYEUPVWOPIM-UHFFFAOYSA-N cinchonidine Natural products C1=CC=C2C(C(C3N4CCC(C(C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-UHFFFAOYSA-N 0.000 description 1
- KMPWYEUPVWOPIM-LSOMNZGLSA-N cinchonine Chemical compound C1=CC=C2C([C@@H]([C@H]3N4CC[C@H]([C@H](C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-LSOMNZGLSA-N 0.000 description 1
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000008282 halocarbons Chemical group 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthesis method of chiral 2,2 '- di-alkoxy-1, 1'-binaphthyl, which comprises the following three steps that: 1. a hydrogen peroxide solution is dropwise added to water, 2 - naphthol and ferric trichloride in stirring at a temperature of 20 to 95 DEG C to be reacted for 3 to 5h, and racemic BINOL(1,1'-Bi-2-naphthol) is filtered out; 2. N-Benzylcinchonidinium chloride is used as a resolving agent, and is reacted with the racemic BINOL in an aprotic solvent to filter out N-Benzylcinchonidinium chloride . R-BINOL molecule compound, the compound is resolved by a mixed liquid of ethyl acetate and hydrochloric acid, and a solvent is steamed out from a solvent layer to obtain R-BINOL; and a filtrate is treated by the mixed liquid of the ethyl acetate and the hydrochloric acid after the solvent is streamed out of the filtrate, and the solvent is steamed out of the solvent layer to obtain S-BINOL; 3. chiral BINOL is respectively reacted with an etherification reagent below a temperature of 127 DEG C to obtain the chiral 2,2 '- di-alkoxy-1, 1'-binaphthyl. The synthesis method has high conversion rate of raw materials and high purity of products, and is an efficient and environmentally friendly process.
Description
Technical field
The invention belongs to chiral binaphthyl substituting group compou nd synthesis scope, relate to chipal compounds intermediate and synthesize, split and difference synthesis of chiral dinaphthalene substitution compound.
Background technology
Z-N (Ziegler-Natta) catalyzer is the important catalyst system of olefinic polymerization.Carrier preparation technology's progress and two processes of the exploitation of internal electron donor have mainly been experienced in its development.ZL 200610054611.X, US7964678B
2report: 2,2 '-dialkoxy-1,1 '-dinaphthalene (claiming again 1,1 '-dinaphthalene-2,2 '-dialkyl ether) is the electron donor of high comprehensive performance.But, what use is racemic modification 2, 2 '-dialkoxy-1, 1 '-dinaphthalene, its Z-N catalyst solid constituent of preparing as internal electron donor is for alpha-olefin polymerization, only when existing, compound internal electron donor just can obtain the polyolefine of high isotactic, if use chirality R-2, 2 '-dialkoxy-1, 1 '-dinaphthalene or S-2, 2 '-dialkoxy-1, 1 '-dinaphthalene is the internal electron donor of Z-N catalyst solid constituent, can when the poly-alpha olefins of the high degree of preparation, save compound internal electron donor? chirality R-2, 2 '-dialkoxy-1, 1 '-dinaphthalene or S-2, 2 '-dialkoxy-1, 1 '-dinaphthalene is the important part of many chiral catalysts.Therefore, prepare highly purified R-2,2 '-dialkoxy-1,1 '-dinaphthalene or S-2,2 '-dialkoxy-1,1 '-dinaphthalene is very significant.At present, yet there are no about preparing two kinds of highly purified R-2,2 '-dialkoxy-1,1 '-dinaphthalene and S-2,2 '-dialkoxy-1, the report of 1 '-dinaphthalene simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of high purity R-1 that first prepares, 1 '-dinaphthalene-2,2 '-diphenol (referred to as R-BINOL, lower same) and S-1,1 '-dinaphthalene-2,2 '-diphenol intermediate (referred to as S-BINOL, lower same), and then preparation high purity R-2,2 '-dialkoxy-1,1 '-dinaphthalene and S-2,2 '-dialkoxy-1, the method for 1 '-dinaphthalene.
Technical scheme of the present invention is: chirality 2, and 2 '-dialkoxy-1, the technology of preparing of 1 '-dinaphthalene (R-2,2 '-dialkoxy-1,1 '-dinaphthalene and S-2,2 '-dialkoxy-1,1 '-dinaphthalene), comprises three-step reaction.
The first step, by iron trichloride be catalyzer, hydrogen peroxide be oxygenant, beta naphthal linked reaction prepare racemic modification BINOL (1,1 '-dinaphthalene-2, the abbreviation of 2 '-diphenol, lower with).It becomes BINOL technological transformation to form by disclosed stoichiometric iron trichloride oxidative coupling beta naphthal, its advantage is that raw material beta naphthal almost all transforms, and no coupling product generates, and is conducive to prepare high purity target product, separating technology is simple, containing the solvent cycle of catalyzer, uses.
Second step, with the new disassemble technique of molecular recognition, by chlorination N-benzyl Xin Kening resolving racemic, BINOL prepares chirality R-BINOL and S-BINOL.By molecular recognition technology, split BINOL, by circulation, split, can obtain highly purified R-BINOL and the S-BINOL of two equivalent, be conducive to postorder synthetic.Meanwhile, R-BINOL and S-BINOL have been widely used, and are the synthetic raw materials of other chipal compounds and are again the parts of important chiral catalyst.
The 3rd step, in the polar solvent that is 5～50 in DIELECTRIC CONSTANT ε, at lower than 127 ℃, by chirality R-BINOL and S-BINOL, react respectively the corresponding chirality R-2 of preparation, 2 '-dialkoxy-1,1 '-dinaphthalene and S-2 with alkali, etherifying reagent, 2 '-dialkoxy-1,1 '-dinaphthalene.R-BINOL or S-BINOL that this step is used are not limited to the R-BINOL and the S-BINOL that by chlorination N-benzyl Xin Kening resolving racemic BINOL, are obtained, can prepare by other method, as chlorination N-benzyl Xin Keniding resolving racemic BINOL, but the necessary high purity that guarantees R-BINOL and S-BINOL.
Concrete synthesis step is:
The preparation of 1 racemic modification BINOL: take water as mark medium, prepare racemic modification BINOL by iron trichloride as catalyzer, hydrogen peroxide as oxygenant, beta naphthal linked reaction.Wherein iron trichloride is Iron(III) chloride hexahydrate, with the mol ratio of beta naphthal be 0.05～3.50; Hydrogen peroxide is industrial goods, and the aqueous solution that its concentration is 30w%～96w% all can be used, and uses the operation of 30w% hydrogen peroxide safer; The mol ratio of hydrogen peroxide and beta naphthal is stoichiometry; The consumption of WATER AS FLOW MEDIUM is the amount doesn't matter, with every mole of beta naphthal, with 2500～3000ml, is advisable.
Concrete steps are: in reactor, add water, beta naphthal, under agitation in 20～95 ℃, drip superoxol, this is a heterogeneous catalytic reaction, reaction times is depended on concentration, beta naphthal size of particles, temperature of reaction of iron trichloride etc., generally in 3～6 hours, beta naphthal almost completely changes into raceme BINOL, byproduct of reaction is water, through simply filtering to isolate racemic modification BINOL, is used as the raw material that second step splits.
In filtrate, contain iron trichloride, can recycle.While recycling, add after beta naphthal, stir as previously mentioned lower 20～95 ℃ and drip superoxols reactions.
The fractionation of 2 raceme BINOL: the chlorination N-benzyl Xin Kening of take is resolving agent, in aprotic solvent, react with racemic modification BINOL, chlorination N-benzyl Xin Kening and racemic modification BINOL mol ratio are 0.5～1: 1, aprotic solvent consumption changes along with solvent property, and generally its consumption is that every mole of racemic modification BINOL is advisable with 2500～3500ml.
Concrete operation step is: in reactor, add raceme BINOL, resolving agent and solvent, under agitation back flow reaction 3～7h.Chlorination N-benzyl Xin Kening and R-BINOL form molecular complex (pungent gram of peaceful R-BINOL of N-benzyl) and are precipitated out from aprotic solvent, and S-BINOL and chlorination N-benzyl Xin Kening do not form molecular complex, are dissolved in aprotic solvent.Reaction is finished, and filters out molecular complex, and at room temperature, pungent gram of peaceful R-BINOL molecular complex of 5g chlorination N-benzyl and ethyl acetate and 1mol/L hydrochloric acid (volume ratio 2: 1) mixed solution 100～140ml are uniformly mixed until solids dissolves.After layering, the solvent steaming except organic layer obtains R-BINOL, and acid layer is in order to reclaim resolving agent; From filtrate, steam aprotic solvent, at room temperature, with aforementioned ethyl acetate and hydrochloric acid mixed solution, process gained solids until dissolve completely, after layering, the solvent steaming except organic layer obtains S-BINOL, and acid layer is in order to reclaim resolving agent; Wash respectively, be dried isolated R-BINOL and S-BINOL.
Be not limited to ethyl acetate and 1mol/L hydrochloric acid (volume ratio 2: 1) mixed solution and decompose chlorination pungent gram of peaceful R-BINOL molecular complex of N-benzyl and treatment S-BINOL solid, other organic solvent/Non-oxidized diluted acid solvents also can be applied, as also fine in butylacetate and dilute sulphuric acid mixed solution, ether/dilute hydrochloric acid mixed solution effect.Ethyl acetate and 1mol/L hydrochloric acid (volume ratio 2: 1) mixed solution, operates more convenient.
Merge diacid layer solution, add sodium hydrogen carbonate solution until chlorination N-benzyl Xin Kening precipitates completely, filter, wash, be dried, reclaim resolving agent chlorination N-benzyl Xin Kening, the rate of recovery is 93%, repeatedly recycles its rate of recovery > 85%, splits efficiency and do not subtract.
When precipitation chlorination N-benzyl Xin Kening, can use the alkaline solutions such as potassium hydroxide, sodium hydroxide, salt of wormwood, sodium carbonate, but gentleer with sodium hydrogen carbonate solution reaction.
Described aprotic solvent is halocarbon, ether, ketone, ester, acid amides, nitrile, the common solvent of nitro-compound, especially easy to use with acetonitrile, ethyl formate, butyl formate, methyl acetate, ethyl acetate or butylacetate, the advantage that ester is made solvent is little to environmental hazard.
The solvent that aprotic solvent splits, R-BINOL once through yield > 75.0%, purity > 99.0%, repeat to split the S-BINOL that purity is lower, can obtain the S-BINOL of purity > 99.0%, two enantiomorphs are separated completely.
The present invention splits in acetonitrile solvent, chlorination N-benzyl Xin Kening and racemic modification BINOL mol ratio are 0.5～1: 1, every mole of racemic modification BINOL, acetonitrile consumption 2750～4500ml, under reflux temperature, react 6h, R-BINOL once through yield 60.0～85.0%, purity > 99.0%, although S-BINOL once through yield is very high, purity is not high.Having optimized splitting condition, is 1: 0.7 at BINOL to resolving agent mol ratio, when every gBINOL adds acetonitrile 10.5ml, R-BINOL once through yield brings up to 85.0%, and purity is that 99.8%, S-BINOL once through yield brings up to 83.1%, purity is 91.2%, exceeds reported in literature value far away.The present invention's protonic solvent, as the split solvent of agent of methyl alcohol, ethanol, the pungent gram of peaceful R-BINOL molecular complex of chlorination N-benzyl obtaining under similarity condition seldom, may be the formation that protonic solvent has disturbed pungent gram of peaceful R-BINOL molecular complex of chlorination N-benzyl.
Resolving agent used in the present invention by benzyl chloride and cinchonine back flow reaction in DMF solution prepare, its yield is up to more than 90%, the specific rotatory power of chlorination N-benzyl Xin Kening is [a]
26=+165 ° of (c=0.003, H
2o), excessive benzyl chloride recycling use.
3 chirality R-2,2 '-dialkoxy-1,1 '-dinaphthalene and S-2,2 '-dialkoxy-1,1 '-dinaphthalene synthetic.In the polar solvent that is 5～50 in DIELECTRIC CONSTANT ε, the R-BINOL of the purity > 99% being split out by second step and S-BINOL react respectively the corresponding highly purified R-2 of preparation with alkali, etherifying reagent, 2 '-dialkoxy-1,1 '-dinaphthalene and S-2,2 '-dialkoxy-1,1 '-dinaphthalene.
Proportioning raw materials is: the mol ratio of chirality BINOL and etherifying reagent is 1: 2～15, with the mol ratio of alkali be 1: 2～15.The chirality BINOL of every mole needs the polar solvent that the DIELECTRIC CONSTANT ε of 1000～2000ml is 5～50, wherein can be by 20～30% for diluting etherifying reagent.
Its concrete steps: prepare in proportion raw material, chirality BINOL, solvent and alkali are placed in to reactor, stirring and dissolving, drip the mixed solution of etherifying reagent and solvent at lower than 127 ℃, with TLC, follow the tracks of reaction, the general reaction times is 0.5～5h, depends on the character of etherifying reagent.React complete filtration, with 1mol/L hydrochloric acid washing leaching cake, then wash twice with water, be dried to obtain S or R-2,2 '-dimethoxy-1,1 '-dinaphthalene.The transformation efficiency of chirality BINOL >=>=99.0%, the purity of product >=>=99.0%, once through yield 91.0～94.0%.
The temperature of etherification reaction, higher than 127 ℃, will be accelerated the racemization speed of chirality thing, the difficult purifying of product, the purity of reduction product.
Wherein: described alkali is sodium hydroxide, potassium hydroxide, sodium carbonate or salt of wormwood;
Described etherifying reagent is: sulfuric acid dialkyl or containing straight or branched C1-C16 uncle haloalkane.Sulfuric acid dialkyl is selected from methyl-sulfate or ethyl sulfate.Straight or branched C1-C16 uncle haloalkane is selected from methyl iodide, iodoethane, iodopropane, butyl iodide, iodine Trimethylmethane, iodopentane, iodine iso-pentane, iodohexane, iodine heptane, iodo-octane, iodine octane-iso, iodine 12 cetyl iodides, monobromethane, monobromethane, N-PROPYLE BROMIDE, bromine isopropyl alkane, n-butyl bromide, bromine Trimethylmethane, bromo pentane silane, bromine iso-pentane, bromohexane, bromine isohexane, heptyl bromide, bromooctane, bromine octane-iso, bromo-dodecane, bromo-tetradecane, bromine n-Hexadecane, methyl chloride, monochloroethane, chloropropane, chlorine iso-propane, chloropropane iso-chlorobutane, chloropentane, chlorine iso-pentane, chlorohexane, chlorine isohexane, chloroheptane, chloro-octane, chlorine octane-iso, chlorodecane, chlorododecane, the chlorine tetradecane, a kind of in chlorine n-Hexadecane.Bromoalkane and alkyl chloride are conventional etherifying reagents, alkyl chloride commercial run preferably.With sulfuric acid dialkyl and bromo C2～C4 nalka, do etherifying reagent, speed of reaction is fast, and the product obtaining can be used as the catalyzer of electron donor synthesizing poly alpha-olefin.
Described solvent is that DIELECTRIC CONSTANT ε is 5～50 polar solvent, common alcohol, ketone, ether, ester, acid amides, sulfone and nitro-compound, mainly to be selected from methyl alcohol, ethanol, Virahol, acetone, butanone, 2 pentanone, propione, ether, propyl ether, methyl tertiary butyl ether, tetrahydrofuran (THF), ethyl formate, methyl acetate, ethyl acetate, butylacetate, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N, a kind of in N-diethylformamide, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide (DMSO), acetonitrile, Nitromethane 99Min..A kind of for well with in acetone, methyl tertiary butyl ether, tetrahydrofuran (THF), ethyl formate, methyl acetate, ethyl acetate, butylacetate, DMF, hexamethylphosphoramide, dimethyl sulfoxide (DMSO), acetonitrile.
Described solvent is that DIELECTRIC CONSTANT ε is 5～50 aprotic solvent, can at 20～60 ℃, drip the mixed solution of etherifying reagent and solvent, and the reaction times is 0.5～2h, in product without racemization component.
The acetone of take at room temperature drips the acetone soln of methyl-sulfate as solvent, and the reaction times is less than 0.5h, chirality 2, and 2 '-dimethoxy-1, the once through yield of 1 '-dinaphthalene is 89.8%.
Use separately a kind of solvent, wherein contain the water that etherification reaction generates, can be not separated.After product separation, solvent does not dewater, and circulation is as the solvent of step (3) etherification reaction, and effect does not subtract.
Outstanding beneficial effect of the present invention is:
1. for to prepare raceme BINOL from beta naphthal oxidative coupling, then split and obtain equivalent chirality BINOL, chirality BINOL etherificate obtains chirality target product.This is that a less energy-consumption high conversion highly selective is prepared chirality 2,2 '-dialkoxy-1, the environmentally friendly technology of 1 '-dinaphthalene fast.
2. in the first step linked reaction, filtrate cycle is used; Second resolving agent rate of recovery is 93%, repeatedly recycles its rate of recovery, splits efficiency and do not subtract; After three-step reaction product separation, solvent does not add refining, and circulation is as the solvent of etherification reaction, and effect does not subtract.There is no waste.
3. chlorination N-benzyl Xin Kening is that resolving agent fractionation BINOL obtains highly purified intermediate product chirality BINOL, is the gordian technique that the present invention breaks through.This has not only met the present invention and has prepared high-purity chiral 2,2 '-dialkoxy-1, the needs of 1 '-dinaphthalene, more importantly provide the fractionation of racemize BINOL to obtain high-purity chiral BINOL practical approach, effective reagent are provided to the purposes of other high-purity chirals BINOL.
4. the gordian technique of another breakthrough of the present invention is to find lower than 127 ℃, 20～60 ℃ of etherification reactions particularly, and salt and the product chirality 2 of raw material chirality BINOL, reaction intermediate chirality BINOL, 2 '-dialkoxy-1,1 '-dinaphthalene is all without racemization phenomenon.This provides reference for take chirality BINOL as raw material synthesis of high purity chiral catalyst and high-purity chiral BINOL derivative.
The invention will be further described below to use embodiment.
Embodiment
Embodiment 1: BINOL is prepared in catalytic oxidation of hydrogen peroxide coupling
In 100ml there-necked flask, add respectively 3.8g FeCl
36H
2o, 40ml water and 2.0g beta naphthal.At 65 ℃ of water-baths, stir, limit coronite drips 30% superoxol, follows the tracks of to react to raw material to disappear with TLC, filters, and washing, obtains needle-like BINOL crystal.In filtrate, add 2.0g2-naphthols again, stir limit coronite and drip 30% superoxol at 65 ℃ of water-baths, follow the tracks of to react to raw material disappear with TLC, filter, washing, obtains BINOL crystal.So repeat experiment.Result is as table 1
The experimental result of table 1 catalytic oxidation of hydrogen peroxide beta naphthal coupling
Embodiment 2: racemize BINOL splits preparation chirality BINOL
In 100ml there-necked flask, add successively purity to reach the 5.72g of 99.7% BINOL, homemade [a]
26=+165 ° of (c=0.003, H
2o) pungent gram of peaceful 6.74g of chlorination N-benzyl, 60ml acetonitrile, stirring reaction 6h under reflux temperature.Filter out pungent gram of peaceful R-BINOL molecular complex of chlorination N-benzyl, at room temperature use 180ml ethyl acetate and 1M hydrochloric acid (volume ratio 2: 1) mixed solution to process pungent gram of peaceful R-BINOL molecular complex of chlorination N-benzyl, the solvent of evaporation organic layer obtains R-BINOL 2.43g, yield 85.0%, acid layer is standby containing resolving agent, reclaims resolving agent.Acetonitrile in vapourisation under reduced pressure filtrate, at room temperature processes solids with 110ml ethyl acetate and hydrochloric acid mixed solution, and the solvent of evaporation organic layer obtains S-BINOL 2.38g, yield 83.1%, and acid layer is standby containing resolving agent, reclaims resolving agent.With HPLC, analyze R-BINOL purity > 99.0% and S-BINOL purity > 91.0%.
Merge diacid layer solution, add the solution of 12.0g sodium bicarbonate, chlorination N-benzyl Xin Kening precipitation, filters, washs, is dried, and obtains pungent gram of peaceful 4.71g of chlorination N-benzyl, the rate of recovery 93%.
Embodiment 3: racemize BINOL splits preparation chirality BINOL
Except ethyl acetate 55ml substitutes 60ml acetonitrile, the other the same as in Example 2, isolates R-BINOL2.13g, purity 99.7%, yield 74.5%.[a] of S-BINOL
20=-28.0 °.
Embodiment 4: racemize BINOL splits preparation chirality BINOL
Except butylacetate 55ml substitutes 60ml acetonitrile, the other the same as in Example 2, isolates R-BINOL2.20g, purity 99.1%, yield 76.9%.[a] of S-BINOL
20=-29.1 °.
Embodiment 5: low-purity S-BINOL circulation splits preparation chirality BINOL
In 100ml there-necked flask, add S-BINOL 2.86g, purity 77.9%, resolving agent 1.27g, ethyl acetate 27ml, its process is with embodiment 2.To the S-BINOL fractionation that circulates, experimental result table 2:
The experiment knot that table 2 low-purity S-BINOL circulation splits
Embodiment 6: reclaim chlorination N-benzyl Xin Kening and split preparation chirality BINOL for racemize BINOL circulation
Except resolving agent reclaims, its process is with embodiment 2.Experimental result is as table 3:
The experimental result of table 3. resolving agent recycle
Embodiment 7:R-2,2 '-dimethoxy-1,1 '-dinaphthalene synthetic
In 100ml there-necked flask, add R-BINOL 2.86g (purity > 99.0%), acetone 15ml, NaOH0.96g, under agitation, drip the mixed solution of methyl-sulfate 3.0g and acetone 5ml, time for adding is 15min, with TLC, analyze and follow the tracks of reaction, in 2h, raw material R-BINOL all transforms, stopped reaction.Filter, with dilute hydrochloric acid 10ml washing leaching cake, then use 10ml water washing twice, be dried to obtain R-2,2 '-dimethoxy-1,1 '-dinaphthalene.Result is as table 4:
Experimental result during table 4 differing temps
The transformation efficiency > 99% that is R-BINOL with HPLC analytical results, R-2,2 '-dimethoxy-1,1 ' dinaphthalene content > 99%.
Embodiment 8:S-2,2 '-dimethoxy-1, the synthetic and acetone recycle utilization of 1 '-dinaphthalene
Except the S-BINOL with purity > 99.0% substitutes 25 ℃ of R-BINOL, temperature of reaction, its process is with embodiment 7.Filter out after product, filtrate cycle is done the dispersion agent of rear primary first-order equation.Result is as table 5:
The experimental result that table 5 acetone recycle is utilized
HPLC analytical results is the transformation efficiency > 99% of S-BINOL, S-2,2 '-dimethoxy-1,1 '-dinaphthalene content > 99.0%.
Embodiment 9:R-2,2 '-dimethoxy-1,1 '-dinaphthalene synthetic
Use the solvent acetone in embodiment 7 instead ethyl acetate, temperature of reaction changes 25 ℃ into, and its process is constant, it is 2.5 hours that R-BINOL transforms the reaction times needing completely, obtains R-2,2 '-dimethoxy-1,1 '-dinaphthalene 2.48g, content > 99.0%.
Embodiment 10:R-2,2 '-dimethoxy-1,1 '-dinaphthalene synthetic
Use the sodium hydroxide in embodiment 7 instead salt of wormwood, temperature of reaction changes 25 ℃ into, and its process is constant, and the time that R-BINOL transforms is completely 4.5 hours, obtains R-2,2 '-dimethoxy-1,1 '-dinaphthalene 2.48g, content > 99.0%.
Embodiment 11:R-2,2 '-dibutoxy-1, the synthetic of 1 '-dinaphthalene used the methyl-sulfate in embodiment 7 instead bromination of n-butane, and its process is constant, obtains R-2,2 '-dibutoxy-1,1 '-dinaphthalene 3.67g, content > 99.0%.
Embodiment 12:R-2,2 '-dimethoxy-1,1 '-dinaphthalene synthetic
Change the acetone in embodiment 7 into butylacetate, its process is constant, obtains R-2,2 '-dimethoxy-1,1 '-dinaphthalene 2.5g, content > 99.0%.
Embodiment 13: the impact of different solvents on etherification reaction
With the operating process in embodiment 7, by acetone, DMF, DMSO, ethyl acetate, respectively at 50 ℃ of etherification reactions, obtain the result of table 6:
Table 6 R-BINOL in different solvents result of methyl-sulfate etherificate
Embodiment 14:
By a small amount of specific rotatory power [a]
17=+35.3 R-BINOL is dissolved in butylacetate, and reflux 0.5-3 hour steams solvent, dry, surveys specific rotation, and result is as table 7.
Table 7R-BINOL racemization experimental result
Embodiment 15:
By a small amount of specific rotation [a]
17the R-2 of=+ 52.0 °, 2 '-dimethoxy-1,1 '-dinaphthalene is dissolved in butylacetate, and reflux 1-3 hour steams solvent, dry, surveys specific rotation, and result is as table 8.
Table 8R-2,2 '-dimethoxy-1, the experimental result of 1 '-dinaphthalene
Claims (10)
1. chirality 2,2 '-dialkoxy-1, and the synthetic method of 1 '-dinaphthalene, is characterized in that the steps include:
(1) preparation of racemic modification BINOL: under water, iron trichloride exist, be that oxygenant carries out linked reaction to beta naphthal and prepares racemic modification BINOL with hydrogen peroxide;
Wherein iron trichloride is Iron(III) chloride hexahydrate, and the mol ratio of Iron(III) chloride hexahydrate and beta naphthal is 0.05～3.50:1; Hydrogen peroxide is the industrial goods aqueous solution, and its concentration is 30w%～96w%, with the mol ratio of beta naphthal be stoichiometry; The consumption of WATER AS FLOW MEDIUM is every mole of 2500～3000ml for beta naphthal;
Concrete steps are: in reactor, add water, beta naphthal and Iron(III) chloride hexahydrate, stir lower 20～95 ℃ and drip superoxol, react 3～6h, filter to isolate racemic modification BINOL;
(2) fractionation of racemize BINOL: the chlorination N-benzyl Xin Kening of take is resolving agent, in aprotic solvent, react with racemic modification BINOL, chlorination N-benzyl Xin Kening and racemic modification BINOL mol ratio are 0.5～1:1, and aprotic solvent consumption is every mole of racemic modification 2500～3500ml for BINOL;
Concrete operation step is: in reactor, add raceme BINOL, resolving agent and solvent, stir lower back flow reaction 3～7h; Reaction is finished, filter out pungent gram of peaceful R-BINOL molecular complex of chlorination N-benzyl, at room temperature, mixed solution 100～140ml of pungent gram of peaceful R-BINOL molecular complex of 5g chlorination N-benzyl and ethyl acetate and 1mol/L hydrochloric acid volume ratio 2:1 is uniformly mixed until solids dissolves, after layering, the solvent steaming except organic layer obtains R-BINOL, and acid layer is in order to reclaim resolving agent; From filtrate, steam aprotic solvent, at room temperature, with aforementioned ethyl acetate and hydrochloric acid mixed solution, process gained solids until dissolve completely, after layering, the solvent steaming except organic layer obtains S-BINOL, and acid layer is in order to reclaim resolving agent; Wash respectively, be dried R-BINOL and S-BINOL; Merge diacid layer solution, add sodium hydrogen carbonate solution until chlorination N-benzyl Xin Kening precipitates completely, filter, wash, be dried, reclaim resolving agent chlorination N-benzyl Xin Kening;
Described aprotic solvent is acetonitrile, ethyl formate, butyl formate, methyl acetate, ethyl acetate or butylacetate;
R-BINOL once through yield > 75.0%, purity > 99.0%;
(3) chirality R-2,2 '-dialkoxy-1,1 '-dinaphthalene and S-2,2 '-dialkoxy-1,1 '-dinaphthalene synthetic: in the polar solvent that is 5～50 in DIELECTRIC CONSTANT ε, the purity > 99.0%R-BINOL being split out by second step and S-BINOL reacts with alkali, etherifying reagent respectively and prepare corresponding highly purified R-2,2 '-dialkoxy-1,1 '-dinaphthalene and S-2,2 '-dialkoxy-1,1 '-dinaphthalene;
Proportioning raw materials is: the mol ratio of chirality BINOL and etherifying reagent is 1:2～15, with the mol ratio of alkali be also 1:2～15; The chirality BINOL of every mole needs the polar solvent that the DIELECTRIC CONSTANT ε of 1000～2000ml is 5～50, and wherein 20～30% for diluting etherifying reagent;
Its concrete steps: chirality BINOL, solvent and alkali are placed in to reactor, and stirring and dissolving, drips the mixed solution of etherifying reagent and solvent at lower than 127 ℃, reaction 0.5～5h, react complete, filter, with 1mol/L hydrochloric acid washing leaching cake, wash with water again twice, be dried to obtain S or R-2,2 '-dialkoxy-1,1 '-dinaphthalene, transformation efficiency >=99.0% of chirality BINOL, purity >=99.0% of product;
Wherein: described alkali is sodium hydroxide, potassium hydroxide, sodium carbonate or salt of wormwood;
Described solvent is that DIELECTRIC CONSTANT ε is 5～50 polar solvent, be selected from methyl alcohol, ethanol, Virahol, acetone, butanone, 2 pentanone, propione, ether, propyl ether, methyl tertiary butyl ether, tetrahydrofuran (THF), ethyl formate, methyl acetate, ethyl acetate, butylacetate, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N, a kind of in N-diethylformamide, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide (DMSO), acetonitrile, Nitromethane 99Min.;
Described etherifying reagent is: sulfuric acid dialkyl or containing straight or branched C1-C16 uncle haloalkane, wherein sulfuric acid dialkyl is selected from methyl-sulfate or ethyl sulfate, straight or branched C1-C16 uncle haloalkane is selected from methyl iodide, iodoethane, iodopropane, butyl iodide, iodine Trimethylmethane, iodopentane, iodine iso-pentane, iodohexane, iodine heptane, iodo-octane, iodine octane-iso, monobromethane, monobromethane, N-PROPYLE BROMIDE, bromine isopropyl alkane, n-butyl bromide, bromine Trimethylmethane, bromo pentane silane, bromine iso-pentane, bromohexane, bromine isohexane, heptyl bromide, bromooctane, bromine octane-iso, bromo-dodecane, bromo-tetradecane, bromine n-Hexadecane, methyl chloride, monochloroethane, chloropropane, chlorine iso-propane, chloropentane, chlorine iso-pentane, chlorohexane, chlorine isohexane, chloroheptane, chloro-octane, chlorine octane-iso, chlorodecane, chlorododecane, the chlorine tetradecane, a kind of in chlorine n-Hexadecane.
2. chirality 2 according to claim 1,2 '-dialkoxy-1, the synthetic method of 1 '-dinaphthalene, is characterized in that in its step (1), filtrate cycle containing catalyzer iron trichloride after filtering is used, then adds beta naphthal, stirring, 20～95 ℃ to drip superoxol reaction.
3. chirality 2 according to claim 1,2 '-dialkoxy-1, the synthetic method of 1 '-dinaphthalene, is characterized in that solvent in its step (2) is that aprotic solvent is selected a kind of in acetonitrile, ethyl acetate, butylacetate.
4. chirality 2 according to claim 1,2 '-dialkoxy-1, the synthetic method of 1 '-dinaphthalene, is characterized in that reclaiming and obtaining resolving agent chlorination N-benzyl Xin Kening in its step (2), repeatedly recycle, its rate of recovery > 85%, fractionation efficiency do not subtract.
5. chirality 2 according to claim 1,2 '-dialkoxy-1, the synthetic method of 1 '-dinaphthalene, it is characterized in that splitting out in its step (2) S-BINOL of purity < 99%, with the method one or many of step (2), repeat to split the S-BINOL that obtains purity > 99.0%.
6. chirality 2 according to claim 1,2 '-dialkoxy-1, the synthetic method of 1 '-dinaphthalene, it is characterized in that the described solvent of its step (3) is a kind of in acetone, methyl tertiary butyl ether, tetrahydrofuran (THF), ethyl formate, methyl acetate, ethyl acetate, butylacetate, DMF, hexamethylphosphoramide, dimethyl sulfoxide (DMSO), acetonitrile.
7. according to chirality described in claim 1 or 62,2 '-dialkoxy-1, the synthetic method of 1 '-dinaphthalene, it is characterized in that solvent described in its step (3) is that DIELECTRIC CONSTANT ε is 5～50 aprotic solvent, at 20～60 ℃, drip the mixed solution of etherifying reagent and solvent, the reaction times is 0.5～2h.
8. chirality 2 according to claim 1,2 '-dialkoxy-1, the synthetic method of 1 '-dinaphthalene, is characterized in that the described solvent of its step (3) is acetone, drips the acetone soln of methyl-sulfate under room temperature, the reaction times is 0.5h.
9. according to chirality 2 described in any one in claim 1,6 or 8,2 '-dialkoxy-1, the synthetic method of 1 '-dinaphthalene, is characterized in that solvent described in its step (3) does not deal with that to be cycled to used in this step product synthetic.
10. chirality 2 according to claim 1,2 '-dialkoxy-1, the synthetic method of 1 '-dinaphthalene, is characterized in that the described etherifying reagent of its step (3) is sulfuric acid dialkyl and bromo C2～C4 alkane.
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