CN101659675B - Regeneration method of triphenylphosphine from waste residue of Wittig reaction - Google Patents
Regeneration method of triphenylphosphine from waste residue of Wittig reaction Download PDFInfo
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- CN101659675B CN101659675B CN2009101524357A CN200910152435A CN101659675B CN 101659675 B CN101659675 B CN 101659675B CN 2009101524357 A CN2009101524357 A CN 2009101524357A CN 200910152435 A CN200910152435 A CN 200910152435A CN 101659675 B CN101659675 B CN 101659675B
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- Prior art keywords
- waste residue
- wittig reaction
- triphenylphosphine
- ether
- reaction waste
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- 239000002699 waste material Substances 0.000 title claims abstract description 88
- 238000007239 Wittig reaction Methods 0.000 title claims abstract description 69
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000011069 regeneration method Methods 0.000 title claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 43
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000004411 aluminium Substances 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001953 recrystallisation Methods 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000012044 organic layer Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000011084 recovery Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- 150000007530 organic bases Chemical class 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 29
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical group C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 28
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims description 23
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 22
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 22
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 9
- 230000001172 regenerating effect Effects 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 6
- -1 YLENE Chemical compound 0.000 claims description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 6
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 229960001701 chloroform Drugs 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- 150000003053 piperidines Chemical class 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 3
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 3
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 3
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 3
- 229940011051 isopropyl acetate Drugs 0.000 claims description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 3
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 claims description 3
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 2
- KNONOKQJACDNOZ-UHFFFAOYSA-N n-ethylethanamine;propan-2-amine Chemical compound CC(C)N.CCNCC KNONOKQJACDNOZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- 230000009977 dual effect Effects 0.000 abstract 1
- 235000021050 feed intake Nutrition 0.000 description 30
- 238000004128 high performance liquid chromatography Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003944 tolyl group Chemical group 0.000 description 6
- HVRLZEKDTUEKQH-NOILCQHBSA-N Olopatadine hydrochloride Chemical compound Cl.C1OC2=CC=C(CC(O)=O)C=C2C(=C/CCN(C)C)\C2=CC=CC=C21 HVRLZEKDTUEKQH-NOILCQHBSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 4
- 229960004340 lacidipine Drugs 0.000 description 4
- 229960003139 olopatadine hydrochloride Drugs 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000009499 Vanilla fragrans Nutrition 0.000 description 3
- 244000263375 Vanilla tahitensis Species 0.000 description 3
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229960003719 cefdinir Drugs 0.000 description 3
- RTXOFQZKPXMALH-GHXIOONMSA-N cefdinir Chemical compound S1C(N)=NC(C(=N\O)\C(=O)N[C@@H]2C(N3C(=C(C=C)CS[C@@H]32)C(O)=O)=O)=C1 RTXOFQZKPXMALH-GHXIOONMSA-N 0.000 description 3
- 229960004069 cefditoren Drugs 0.000 description 3
- KMIPKYQIOVAHOP-YLGJWRNMSA-N cefditoren Chemical compound S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)\C(=N/OC)C=2N=C(N)SC=2)CC=1\C=C/C=1SC=NC=1C KMIPKYQIOVAHOP-YLGJWRNMSA-N 0.000 description 3
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- 244000277360 Bruguiera gymnorhiza Species 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- LUKBXSAWLPMMSZ-OWOJBTEDSA-N Trans-resveratrol Chemical compound C1=CC(O)=CC=C1\C=C\C1=CC(O)=CC(O)=C1 LUKBXSAWLPMMSZ-OWOJBTEDSA-N 0.000 description 2
- 229940043232 butyl acetate Drugs 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical group CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 235000018991 trans-resveratrol Nutrition 0.000 description 2
- LIBASNWCFRYHQB-UHFFFAOYSA-N (2,3-dichlorophenyl)-diphenylphosphane Chemical compound ClC1=CC=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1Cl LIBASNWCFRYHQB-UHFFFAOYSA-N 0.000 description 1
- VEEGZPWAAPPXRB-BJMVGYQFSA-N (3e)-3-(1h-imidazol-5-ylmethylidene)-1h-indol-2-one Chemical compound O=C1NC2=CC=CC=C2\C1=C/C1=CN=CN1 VEEGZPWAAPPXRB-BJMVGYQFSA-N 0.000 description 1
- DQGBSPYYYCIELK-UHFFFAOYSA-N 1,1-bis(sulfanylidene)-1,3-benzothiazole Chemical compound C1=CC=C2S(=S)(=S)C=NC2=C1 DQGBSPYYYCIELK-UHFFFAOYSA-N 0.000 description 1
- 229940127291 Calcium channel antagonist Drugs 0.000 description 1
- 229940121710 HMGCoA reductase inhibitor Drugs 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229940121369 angiogenesis inhibitor Drugs 0.000 description 1
- 239000004037 angiogenesis inhibitor Substances 0.000 description 1
- 239000000043 antiallergic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000480 calcium channel blocker Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 239000002471 hydroxymethylglutaryl coenzyme A reductase inhibitor Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009719 regenerative response Effects 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a regeneration method of triphenylphosphine from waste residue of Wittig reaction, which comprises the steps of: (1) dissolving the waste residue of Wittig reaction in an organic solvent A at room temperature, adding aqueous solution of inorganic alkali, insulating, mixing and reacting for 0.5 to 3 hours, and then separating the organic layer; (2) adding inorganic alkali in the organic layer obtained in Step (1), slowly dropwise adding an organic solvent B containing dual(-trichloromethyl) carbonate at the temperature of minus 30 to 90 DEG C, insulating, mixing and reacting for 1 to 6 hours, then adding aluminium powder at the temperature of minus 30 to 90 DEG C, insulating, mixing and reacting for 1 to 6 hours, then dropwise adding diluted hydrochloric acid of 0.1 to 15 percent, conducting decompressed solvent recovery to the separated organic layer, and then conducting recrystallization on residues, thus obtaining the triphenylphosphine. The regeneration method of triphenylphosphine from waste residue of Wittig reaction has the advantages of simple and convenient operation, moderate reaction conditions, easy-controlled production safety, higher reaction yield, high purity of products, low material consumption and low amount of three wastes, with easy process, etc.
Description
(1) technical field
The present invention relates to a kind of method of the triphenylphosphine of from the Wittig reaction waste residue, regenerating.
(2) background technology
The Wittig reaction is an important method of synthetic alkene; In medicine and midbody are synthetic, brought into play vital role, all related to the Wittig reaction like the preparation of medicine such as angiogenesis inhibitor CA-4, anti-allergy agent Olopatadine hydrochloride, β-Nei Xiananleikangshengsu Prozef, cefditoren, calcium antagonist Lacidipine (62, HMG-CoA reductase inhibitor and midbody.In photoelectric functional material, white dyes, sugar charcoal glycosides synthetic, also be widely used in addition.Phosphorus ylide is as one type of important Wittig reagent, and triphenylphosphine in the Wittig reaction process (TPP) is converted into by product triphenylphosphine oxide (TPPO), though the market value of TPPO is higher than TPP; But because of purposes is wideless, demand is little, and present most enterprises lack effectively recovery TPPO and regeneration TPP technology; Often as the waste residue burning disposal; Cause that serious environmental is polluted, disposal of three wastes difficulty is bigger, production cost is higher, and Atom economy is relatively poor.Though in some building-up reactions, can substitute triphenylphosphine by triethyl-phosphite, to reduce cost, recycle yet the by product triethyl phosphate that is produced is very difficult, also do not see the report that recycling is arranged at present.
It is to utilize from spent catalyst to begin one's study and increase gradually that the triphenylphosphine oxide reduction method prepares triphenylphosphine again, but used reductive agent, like LiAlH
4-CeCl
3, SmI
2, S+Pd/C, HSiCl
3Deng, either price is more expensive, or reaction conditions is very harsh, the general requirement high temperature and high pressure.Thasan in 2002 etc. have reported that with acetonitrile, benzene be solvent, make triphenylphosphine through the electrochemical reduction triphenylphosphine oxide, and yield 71% (Thasan, R.et al.Indian Pat., 2002DE00793,2007-4-27.).Though this method condition is gentle, yield is on the low side.2008 year clocks are that intelligent grade discloses the method (CN101357908) that " one kettle way " prepares triphenylphosphine and two (benzothiazole) disulfide, and this method is mainly used in cephalo series active ester and prepares by product triphenylphosphine oxide and the recycling of 2-mercaptobenzothiazole in the process.
(3) summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, provide a kind of easy and simple to handle, reaction conditions is gentle, with short production cycle, production safety is easy to control, reaction yield is higher, product purity is high, material consumption is few, the three wastes are few and easy-to-handle from the Wittig reaction waste residue method of regeneration triphenylphosphine.
The present invention intends and adopts following technical scheme:
A kind of method of the triphenylphosphine of from the Wittig reaction waste residue, regenerating comprises the steps:
(1) under the room temperature Wittig reaction waste residue is placed organic solvent A, behind the aqueous solution of adding mineral alkali, insulation reaction was told organic layer to remove acidic substance wherein in 0.5～3 hour then;
(2) in the organic layer of step (1) gained, add organic bases under the room temperature; Slowly drip the organic solvent B solution that contains two (trichloromethyl) carbonic ethers then ,-30～90 ℃ of following insulation reaction added aluminium powder after 1～8 hour;-30～90 ℃ of following insulation reaction are after 1～6 hour; Drip 0.1～15% Hydrogen chloride again and remove the unnecessary aluminium powder and the aluminum chloride of generation, the organic layer decompression and solvent recovery of telling, residue gets triphenylphosphine through recrystallization;
Wittig reaction waste residue of the present invention is meant the waste residue that when bulk drug such as Wittig prepared in reaction vanilla acid amides, cefdinir, Prozef, cefditoren, Olopatadine hydrochloride, Bruguiera conjugata alcohol first, trans-resveratrol, Lacidipine (62 or midbody, produces; Wherein the quality percentage composition of triphenylphosphine oxide is 30～95%, contains one or more impurity such as season phosphonium salt, organic acid in addition.
The present invention recommends described Wittig reaction waste residue: two (trichloromethyl) carbonic ether: organic bases: the mass ratio that feeds intake of aluminium powder is 1.0: 0.1～0.5: 0.01～0.1: 0.02～0.2, be preferably 1.0: 0.2～0.4: 0.04～0.06: 0.08～and 0.12.The consumption of described organic solvent A is feed intake 1～10 times of quality of Wittig reaction waste residue, preferred 4～7 times; The consumption of described organic solvent B is feed intake 1～10 times of quality of Wittig reaction waste residue, preferred 2～4 times.
The present invention recommends described organic solvent A and organic solvent B independently to be selected from following a kind of or any several kinds combination separately: methylene dichloride, trichloromethane, 1,2-ethylene dichloride, THF, 2-methyltetrahydrofuran, toluene, ethylbenzene, isopropyl benzene, YLENE, chlorobenzene, Skellysolve A, normal hexane, hexanaphthene, methylcyclohexane, ether, positive propyl ether, isopropyl ether, n-butyl ether, methyl-phenoxide, phenyl ethyl ether, three fourth MEEs, ethyl formate, methyl acetate, ETHYLE ACETATE, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate.
It is one of following further to recommend described organic solvent A and organic solvent B independently to be selected from separately: toluene, methylene dichloride, ETHYLE ACETATE.
" separately independent " of the present invention means organic solvent A and not interdependence of organic solvent B, and be relatively independent, can be identical also can be inequality.
It is one of following that organic bases of the present invention can be selected from: triethylamine, Tri-n-Propylamine, tri-isopropyl amine, diethylammonium Isopropylamine, tri-n-butylamine, triethylene diamine, pyridine, 2-picoline, 3-picoline, 4-picoline, piperidines, N; Dinethylformamide, quinoline, N; Accelerine, N; N-Diethyl Aniline, N, N-dimethylamino-4-pyridine, N-methylpyrrole, N-Methylimidazole, N-methylmorpholine; Preferred described organic bases is one of following: triethylamine, pyridine.
The sodium hydroxide solution of the aqueous solution preferred mass mark 1～30% of the described mineral alkali of step of the present invention (1), more preferably 5% aqueous sodium hydroxide solution.The concrete described step (1) of recommending is according to carrying out as follows: under the room temperature Wittig reaction waste residue is dissolved in the organic solvent A, adds 1～30% aqueous sodium hydroxide solution, organic layer is told in insulated and stirred reaction 1～2 hour then.Recommend said Wittig reaction waste residue: the mass ratio that feeds intake of 1～30% sodium hydroxide solution is 1: 1.0～5.0, preferred 1.0: 1.5～3.0.
Step of the present invention (2) can be divided into the reaction in two stages with the line of delimitation that is incorporated as of aluminium powder, and the temperature of reaction of preferred fs is-10～40 ℃, and the reaction times is 2～4h; The temperature of reaction of preferred subordinate phase is 40～80 ℃, and the reaction times is 2～4h.
The present invention drips the Hydrogen chloride of massfraction 0.1～15% after the subordinate phase reaction is accomplished; Be used to remove the unnecessary aluminium powder and the aluminum chloride of generation; Preferred 10% the Hydrogen chloride that uses; Recommend described Wittig reaction waste residue: the mass ratio that feeds intake of 10% Hydrogen chloride is 1.0: 0.2～2.0, be preferably 1.0: 0.5～and 1.0.
The recrystallization solvent that recrystallization of the present invention uses can be selected from following a kind of or any several kinds arbitrary combination: the alcohol of C1～C6, sherwood oil, ether, acetone, toluene, chlorobenzene, YLENE; One of preferred following: Virahol, chlorobenzene.
The present invention is concrete to recommend described renovation process to be undertaken by following sequential steps:
(1) at room temperature the Wittig reaction waste residue is placed toluene, add 5% aqueous sodium hydroxide solution, insulation reaction 1～2 hour is told organic layer then; Described Wittig reaction waste residue: the mass ratio that feeds intake of 5% aqueous sodium hydroxide solution is preferably 1.0: 1.5～and 3.0; The consumption of said toluene is feed intake 4～7 times of quality of Wittig reaction waste residue;
(2) in the organic layer of step (1) gained, add triethylamine; Slowly drip the toluene solution that contains two (trichloromethyl) carbonic ethers then ,-10～40 ℃ of following insulation reaction added aluminium powder after 2～4 hours; 40～80 ℃ of following insulation reaction are after 2～4 hours; Drip 10% Hydrogen chloride again, behind the organic layer decompression and solvent recovery of telling, residue gets triphenylphosphine with the Virahol recrystallization; Described Wittig reaction waste residue: two (trichloromethyl) carbonic ether: triethylamine: aluminium powder: the mass ratio that feeds intake of 10% Hydrogen chloride is preferably 1.0: 0.2～and 0.4: 0.04～0.06: 0.08～0.12: 0.5～1.0; The consumption that contains the toluene in the toluene solution of two (trichloromethyl) carbonic ethers is feed intake 2～4 times of quality of Wittig reaction waste residue.
The present invention compared with prior art, its innovative point is:
A) traditional technology generally reclaims from the Wittig reaction waste residue and refining the pure article of triphenylphosphine oxide, is used for regenerative response then; The present invention then participates in reaction directly with extracting the organic solution obtain containing triphenylphosphine oxide in the Wittig reaction waste residue, has simplified operation sequence greatly, has reduced production cost;
B) adopt two (trichloromethyl) carbonic ethers (BTC) that triphenylphosphine oxide is converted into the dichloro triphenylphosphine, make triphenylphosphine through aluminum reduction then.The present invention has that low in raw material cost is easy to get, reaction conditions is gentle, easy and simple to handle, with short production cycle, yield is higher, the three wastes are few and be easy to advantages such as processing;
C) solve the Wittig reaction waste residue because of being difficult to utilize the problems such as environmental pollution that cause, reached the purpose that turns waste into wealth.
Beneficial effect of the present invention is mainly reflected in: with the simply dealt Wittig reaction waste residue of process is raw material; Need not the refining pure article of triphenylphosphine oxide that obtain; The organic solution that directly will contain triphenylphosphine oxide is participated in chlorination; Obtain triphenylphosphine through aluminum reduction again, the method for preparing triphenylphosphine that a low in raw material cost is easy to get, reaction conditions is gentle, easy and simple to handle, yield is higher, with short production cycle is provided, solved the Wittig reaction waste residue because of being difficult to utilize the problems such as environmental pollution that cause; Reach the purpose that turns waste into wealth, thereby had bigger implementary value and potential economic results in society.
(4) specific embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto.
Embodiment 1
(1) under the room temperature toward Wittig waste residue (the TPPO mass percent is 50%) 200g, toluene 1000g, the 5%NaOH aqueous solution 300g that adds in the churned mechanically 2L there-necked flask in the Prozef production process being housed, 3 hours (t of insulated and stirred reaction
0) after, tell toluene layer;
(2), the 2L four-hole boiling flask of TM, mechanical stirring, constant pressure funnel adds toluene solution, the pyridine (1.0g) of step (1) gained in being housed ,-10 ℃ of (T
1) the slow down solution that contains two (trichloromethyl) carbonic ethers (40.0g) and methylene dichloride (600g) composition, 4 hours (t of insulation reaction of dripping
1) after, add aluminium powder (12.0g), 30 ℃ of (T
2) following 6 hours (t of insulation reaction
2) after, drip 10% Hydrogen chloride (80g) again, tell organic layer, behind the organic layer decompression and solvent recovery, residue gets triphenylphosphine 84.9g with the Virahol recrystallization, yield 90.1%, fusing point 80.0-80.2 ℃, HPLC purity 98.8%.
Embodiment 2
The mass ratio that feeds intake is the Wittig waste residue (the TPPO mass percent is 30%) in the vanilla acid amides production process: 5% aqueous sodium hydroxide solution: two (trichloromethyl) carbonic ether: organic bases: aluminium powder: 10% Hydrogen chloride=1.0: 2.0: 0.1: 0.04: 0.02: 0.8; Organic bases is a triethylamine; Step (1) organic solvent A is a chlorobenzene, and consumption is feed intake 2 times of quality of Wittig reaction waste residue; Step (2) organic solvent B is a THF, and consumption is feed intake 5 times of quality of Wittig reaction waste residue; t
0=0.5h; T
1=-30 ℃, t
1=6h; T
2=60 ℃, t
2=3h; Recrystallization solvent is a propyl carbinol.
Other is with embodiment 1, and TPP yield 81.3%, fusing point are 80.1-80.4 ℃, HPLC purity 98.8%.
Embodiment 3
The mass ratio that feeds intake is the Wittig waste residue (the TPPO mass percent is 60%) in the Prozef production process: 5% aqueous sodium hydroxide solution: two (trichloromethyl) carbonic ether: organic bases: aluminium powder: 10% Hydrogen chloride=1.0: 3.0: 0.25: 0.1: 0.04: 0.3; Organic bases is N, the N-Diethyl Aniline; Step (1) organic solvent A is a methylene dichloride, and consumption is feed intake 6 times of quality of Wittig reaction waste residue; Step (2) organic solvent B is a toluene, and consumption is feed intake 1 times of quality of Wittig reaction waste residue; t
0=1h; T
1=10 ℃, t
1=2h; T
2=-10 ℃, t
2=4h; Recrystallization solvent is a methyl alcohol.
Other is with embodiment 1, and TPP yield 83.2%, fusing point are 80.0-80.3 ℃, HPLC purity 99.0%.
Embodiment 4
The mass ratio that feeds intake is the Wittig waste residue (the TPPO mass percent is 80%) in the cefdinir production process: 5% aqueous sodium hydroxide solution: two (trichloromethyl) carbonic ether: organic bases: aluminium powder: 10% Hydrogen chloride=1.0: 4.0: 0.3: 0.02: 0.12: 1.5; Organic bases is a tri-isopropyl amine; Step (1) organic solvent A is an ETHYLE ACETATE, and consumption is feed intake 4 times of quality of Wittig reaction waste residue; Step (2) organic solvent B is an ETHYLE ACETATE, and consumption is feed intake 7 times of quality of Wittig reaction waste residue; t
0=1.5h; T
1=50 ℃, t
1=8h; T
2=50 ℃, t
2=2h; Recrystallization solvent is an ethanol.
Other is with embodiment 1, and TPP yield 79.0%, fusing point are 80.3-80.5 ℃, HPLC purity 98.7%.
Embodiment 5
The mass ratio that feeds intake is the Wittig waste residue (the TPPO mass percent is 95%) in the Prozef production process: 5% aqueous sodium hydroxide solution: two (trichloromethyl) carbonic ether: organic bases: aluminium powder: 10% Hydrogen chloride=1.0: 5.0: 0.5: 0.01: 0.2: 1.6; Organic bases is a N-methylmorpholine; Step (1) organic solvent A is a YLENE, and consumption is feed intake 3 times of quality of Wittig reaction waste residue; Step (2) organic solvent B is a butylacetate, and consumption is feed intake 4 times of quality of Wittig reaction waste residue; t
0=2h; T
1=60 ℃, t
1=3h; T
2=20 ℃, t
2=6h; Recrystallization solvent is a toluene.
Other is with embodiment 1, and TPP yield 89.6%, fusing point are 80.4-80.5 ℃, HPLC purity 99.1%.
Embodiment 6
The mass ratio that feeds intake is the Wittig waste residue (the TPPO mass percent is 50%) in the Olopatadine hydrochloride production process: 5% aqueous sodium hydroxide solution: two (trichloromethyl) carbonic ether: organic bases: aluminium powder: 10% Hydrogen chloride=1.0: 1.5: 0.3: 0.03: 0.1: 0.7; Organic bases is N, dinethylformamide; Step (1) organic solvent A is the 2-methyltetrahydrofuran, and consumption is feed intake 8 times of quality of Wittig reaction waste residue; Step (2) organic solvent B is the 2-methyltetrahydrofuran, and consumption is feed intake 6 times of quality of Wittig reaction waste residue; t
0=2.5h; T
1=70 ℃, t
1=3h; T
2=50 ℃, t
2=1h; Recrystallization solvent is a n-propyl alcohol.
Other is with embodiment 1, and TPP yield 65.0%, fusing point are 79.8-80.2 ℃, HPLC purity 99.2%.
Embodiment 7
The mass ratio that feeds intake is the Wittig waste residue (the TPPO mass percent is 80%) in the Olopatadine hydrochloride production process: 5% aqueous sodium hydroxide solution: two (trichloromethyl) carbonic ether: organic bases: aluminium powder: 10% Hydrogen chloride=1.0: 2.5: 0.15: 0.06: 0.09: 2.0; Organic bases is a piperidines; Step (1) organic solvent A is a positive propyl ether, and consumption is feed intake 6 times of quality of Wittig reaction waste residue; Step (2) organic solvent B is a chlorobenzene, and consumption is feed intake 2 times of quality of Wittig reaction waste residue; t
0=3h; T
1=-10 ℃, t
1=2h; T
2=70 ℃, t
2=2h; Recrystallization solvent is a chlorobenzene.
Other is with embodiment 1, and TPP yield 72.8%, fusing point are 80.0-80.4 ℃, HPLC purity 98.9%.
Embodiment 8
The mass ratio that feeds intake is the Wittig waste residue (the TPPO mass percent is 30%) in the Bruguiera conjugata alcohol first production process: 5% aqueous sodium hydroxide solution: two (trichloromethyl) carbonic ether: organic bases: aluminium powder: 10% Hydrogen chloride=1.0: 3.5: 0.2: 0.03: 0.05: 0.9; Organic bases is a triethylene diamine; Step (1) organic solvent A is a methyl-phenoxide, and consumption is feed intake 9 times of quality of Wittig reaction waste residue; Step (2) organic solvent B is a YLENE, and consumption is feed intake 4 times of quality of Wittig reaction waste residue; t
0=1h; T
1=50 ℃, t
1=5h; T
2=90 ℃, t
2=2h; Recrystallization solvent is a n-propyl alcohol.
Other is with embodiment 1, and TPP yield 66.0%, fusing point are 80.2-80.6 ℃, HPLC purity 98.8%.
Embodiment 9
The mass ratio that feeds intake is the Wittig waste residue (the TPPO mass percent is 95%) in the vanilla acid amides production process: 5% aqueous sodium hydroxide solution: two (trichloromethyl) carbonic ether: organic bases: aluminium powder: 10% Hydrogen chloride=1.0: 4.5: 0.3: 0.08: 0.15: 1.1; Organic bases is a piperidines; Step (1) organic solvent A is a hexanaphthene, and consumption is feed intake 10 times of quality of Wittig reaction waste residue; Step (2) organic solvent B is a toluene, and consumption is feed intake 3 times of quality of Wittig reaction waste residue; t
0=1.5h; T
1=20 ℃, t
1=1h; T
2=20 ℃, t
2=6h; Recrystallization solvent is an ethanol.
Other is with embodiment 1, and TPP yield 74.8%, fusing point are 79.8-80.2 ℃, HPLC purity 99.2%.
Embodiment 10
The mass ratio that feeds intake is the Wittig waste residue (the TPPO mass percent is 30%) in the trans-resveratrol production process: 5% aqueous sodium hydroxide solution: two (trichloromethyl) carbonic ether: organic bases: aluminium powder: 10% Hydrogen chloride=1.0: 1.5: 0.4: 0.05: 0.13: 1.0; Organic bases is the 3-picoline; Step (1) organic solvent A is 1, the 2-ethylene dichloride, and consumption is feed intake 7 times of quality of Wittig reaction waste residue; Step (2) organic solvent B is a methylene dichloride, and consumption is feed intake 10 times of quality of Wittig reaction waste residue; t
0=2h; T
1=30 ℃, t
1=7h; T
2=-30 ℃, t
2=5h; Recrystallization solvent is a Virahol.
Other is with embodiment 1, and TPP yield 78.5%, fusing point are 80.2-80.5 ℃, HPLC purity 98.6%.
Embodiment 11
The mass ratio that feeds intake is the Wittig waste residue (the TPPO mass percent is 90%) in the Lacidipine (62 production process: 5% aqueous sodium hydroxide solution: two (trichloromethyl) carbonic ether: organic bases: aluminium powder: 10% Hydrogen chloride=1.0: 3.0: 0.5: 0.07: 0.08: 1.4; Organic bases is the N-Methylimidazole; Step (1) organic solvent A is a toluene, and consumption is feed intake 2 times of quality of Wittig reaction waste residue; Step (2) organic solvent B is a toluene, and consumption is feed intake 6 times of quality of Wittig reaction waste residue; t
0=1.5h; T
1=90 ℃, t
1=2h; T
2=80 ℃, t
2=4h; Recrystallization solvent is a sherwood oil.
Other is with embodiment 1, and TPP yield 83.4%, fusing point are 80.0～80.2 ℃, HPLC purity 99.2%.
Embodiment 12
The mass ratio that feeds intake is the Wittig waste residue (the TPPO mass percent is 60%) in the Lacidipine (62 production process: 5% aqueous sodium hydroxide solution: two (trichloromethyl) carbonic ether: organic bases: aluminium powder: 10% Hydrogen chloride=1.0: 2.0: 0.35: 0.09: 0.09: 1.3; Organic bases is a tri-n-butylamine; Step (1) organic solvent A is a butylacetate, and consumption is feed intake 5 times of quality of Wittig reaction waste residue; Step (2) organic solvent B is a toluene, and consumption is feed intake 6 times of quality of Wittig reaction waste residue; t
0=0.5h; T
1=40 ℃, t
1=5h; T
2=60 ℃, t
2=3h; Recrystallization solvent is a methyl alcohol.
Other is with embodiment 1, and TPP yield 71.5%, fusing point are 79.8～80.1 ℃, HPLC purity 99.4%.
Embodiment 13
The mass ratio that feeds intake is the Wittig waste residue (the TPPO mass percent is 40%) in the cefditoren production process: 5% aqueous sodium hydroxide solution: two (trichloromethyl) carbonic ether: organic bases: aluminium powder: 10% Hydrogen chloride=1.0: 4.0: 0.3: 0.06: 0.07: 0.2; Organic bases is N, N-dimethylamino-4-pyridine; Step (1) organic solvent A is a methylene dichloride, and consumption is feed intake 1 times of quality of Wittig reaction waste residue; Step (2) organic solvent B is a chlorobenzene, and consumption is feed intake 5 times of quality of Wittig reaction waste residue; t
0=2h; T
1=40 ℃, t
1=3h; T
2=10 ℃, t
2=1h; Recrystallization solvent is a sherwood oil.
Other is with embodiment 1, and TPP yield 87.0%, fusing point are 79.9～80.2 ℃, HPLC purity 99.5%.
Embodiment 14
The mass ratio that feeds intake is the Wittig waste residue (the TPPO mass percent is 50%) in the cefdinir production process: 5% aqueous sodium hydroxide solution: two (trichloromethyl) carbonic ether: organic bases: aluminium powder: 10% Hydrogen chloride=1.0: 2.5: 0.4: 0.02: 0.17: 0.5; Organic bases is the N-methylpyrrole; Step (1) organic solvent A is a trichloromethane, and consumption is feed intake 3 times of quality of Wittig reaction waste residue; Step (2) organic solvent B is a trichloromethane, and consumption is feed intake 2 times of quality of Wittig reaction waste residue; t
0=1.5h; T
1=0 ℃, t
1=6h; T
2=40 ℃, t
2=1h; Recrystallization solvent is a toluene.
Other is with embodiment 1, and TPP yield 85.9%, fusing point are 80.1～80.3 ℃, HPLC purity 99.2%.
Claims (9)
1. the method for a regeneration triphenylphosphine from the Wittig reaction waste residue is characterized in that comprising the steps:
(1) under the room temperature Wittig reaction waste residue is placed organic solvent A, behind the aqueous solution of adding mineral alkali, insulation reaction 0.5～3 hour is told organic layer then; The quality percentage composition of triphenylphosphine oxide is 30～95% in the described Wittig reaction waste residue; Described organic solvent A is selected from following a kind of or any several kinds combination: methylene dichloride, trichloromethane, 1,2-ethylene dichloride, THF, 2-methyltetrahydrofuran, toluene, ethylbenzene, isopropyl benzene, YLENE, chlorobenzene, Skellysolve A, normal hexane, hexanaphthene, methylcyclohexane, ether, positive propyl ether, isopropyl ether, n-butyl ether, methyl-phenoxide, phenyl ethyl ether, three fourth MEEs, ethyl formate, methyl acetate, ETHYLE ACETATE, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate;
(2) in the organic layer of step (1) gained, add organic bases, slowly drip the organic solvent B solution that contains two (trichloromethyl) carbonic ethers then ,-30～90 ℃ of following insulation reaction are after 1～8 hour; Add aluminium powder;-30～90 ℃ of following insulation reaction drip 0.1～15% Hydrogen chloride after 1～6 hour again, tell organic layer then; Behind the decompression and solvent recovery, residue gets triphenylphosphine through recrystallization; Described Wittig reaction waste residue: two (trichloromethyl) carbonic ether: organic bases: the mass ratio that feeds intake of aluminium powder is 1.0: 0.1～0.5: 0.01～0.1: 0.02～0.2; Described organic solvent B is selected from following a kind of or any several kinds combination: methylene dichloride, trichloromethane, 1,2-ethylene dichloride, THF, 2-methyltetrahydrofuran, toluene, ethylbenzene, isopropyl benzene, YLENE, chlorobenzene, Skellysolve A, normal hexane, hexanaphthene, methylcyclohexane, ether, positive propyl ether, isopropyl ether, n-butyl ether, methyl-phenoxide, phenyl ethyl ether, three fourth MEEs, ethyl formate, methyl acetate, ETHYLE ACETATE, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate.
2. the method for the triphenylphosphine of from the Wittig reaction waste residue, regenerating as claimed in claim 1; It is characterized in that described organic bases is one of following: triethylamine, Tri-n-Propylamine, tri-isopropyl amine, diethylammonium Isopropylamine, tri-n-butylamine, triethylene diamine, pyridine, 2-picoline, 3-picoline, 4-picoline, piperidines, quinoline, N; Accelerine, N; N-Diethyl Aniline, N, N-dimethylamino-4-pyridine, N-methylpyrrole, N-Methylimidazole, N-methylmorpholine.
3. the method for the triphenylphosphine of from the Wittig reaction waste residue, regenerating as claimed in claim 1 is characterized in that the aqueous solution of the described mineral alkali of step (1) is 1～30% aqueous sodium hydroxide solution.
4. the method for the triphenylphosphine of from the Wittig reaction waste residue, regenerating as claimed in claim 3, it is characterized in that the Wittig reaction waste residue: the mass ratio that feeds intake of 1～30% sodium hydroxide solution is 1: 1.0～5.0.
5. the method for the triphenylphosphine of from the Wittig reaction waste residue, regenerating as claimed in claim 1, it is characterized in that described Wittig reaction waste residue: two (trichloromethyl) carbonic ether: organic bases: the mass ratio that feeds intake of aluminium powder is 1.0: 0.2～0.4: 0.04～0.06: 0.08～0.12.
6. the method for the triphenylphosphine of from the Wittig reaction waste residue, regenerating as claimed in claim 1 is characterized in that step (2) before adding aluminium powder, and said reaction is carried out 2～4h at-10～40 ℃ earlier.
7. as claimed in claim 1 from the Wittig reaction waste residue method of regeneration triphenylphosphine, it is characterized in that in the step (2) after adding aluminium powder, in 40～80 ℃ of reaction 2～4h, drip 0.1～15% Hydrogen chloride again.
8. the method for the triphenylphosphine of from the Wittig reaction waste residue, regenerating as claimed in claim 1 is characterized in that the recrystallization solvent that described recrystallization uses is selected from following a kind of or any several kinds arbitrary combination: the alcohol of C1～C6, sherwood oil, ether, acetone, toluene, chlorobenzene, YLENE.
9. as claimed in claim 8 from the Wittig reaction waste residue method of regeneration triphenylphosphine, it is characterized in that described recrystallization solvent is one of following: Virahol, chlorobenzene.
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|---|---|---|---|---|
| GB1029924A (en) * | 1964-02-03 | 1966-05-18 | M & T Chemicals Inc | Process for the production of trihydrocarbon phosphorous compounds |
| US5527966A (en) * | 1993-08-11 | 1996-06-18 | Basf Aktiengesellschaft | Preparation of triphenylphosphine |
| CN101357908A (en) * | 2008-09-04 | 2009-02-04 | 浙江工业大学 | Bisbenzothiazole disulfide and triphenylphosphine preparation by means of one pot |
| CN101481389A (en) * | 2009-01-15 | 2009-07-15 | 宁波工程学院 | Method for recycling triphenyl phosphine oxide and triphenylphosphine from waste slag |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1029924A (en) * | 1964-02-03 | 1966-05-18 | M & T Chemicals Inc | Process for the production of trihydrocarbon phosphorous compounds |
| US5527966A (en) * | 1993-08-11 | 1996-06-18 | Basf Aktiengesellschaft | Preparation of triphenylphosphine |
| CN101357908A (en) * | 2008-09-04 | 2009-02-04 | 浙江工业大学 | Bisbenzothiazole disulfide and triphenylphosphine preparation by means of one pot |
| CN101481389A (en) * | 2009-01-15 | 2009-07-15 | 宁波工程学院 | Method for recycling triphenyl phosphine oxide and triphenylphosphine from waste slag |
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