CN113620990A - 一种硫脲型氮膦配体及其制备方法和应用 - Google Patents
一种硫脲型氮膦配体及其制备方法和应用 Download PDFInfo
- Publication number
- CN113620990A CN113620990A CN202111003484.1A CN202111003484A CN113620990A CN 113620990 A CN113620990 A CN 113620990A CN 202111003484 A CN202111003484 A CN 202111003484A CN 113620990 A CN113620990 A CN 113620990A
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- China
- Prior art keywords
- palladium
- bis
- ligand
- thiourea
- phosphine
- Prior art date
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Links
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000003446 ligand Substances 0.000 title claims abstract description 55
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 48
- KUXDQQMEFBFTGX-UHFFFAOYSA-N [N].P Chemical compound [N].P KUXDQQMEFBFTGX-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 42
- -1 aryl isothiocyanate Chemical class 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 112
- 229910052763 palladium Inorganic materials 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 150000002540 isothiocyanates Chemical class 0.000 claims description 14
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 13
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 10
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 claims description 9
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-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
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- YHYGSIBXYYKYFB-VOTSOKGWSA-N (2e)-octa-2,7-dien-1-ol Chemical compound OC\C=C\CCCC=C YHYGSIBXYYKYFB-VOTSOKGWSA-N 0.000 claims description 7
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical class P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 7
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- RBCARPJOEUEZLS-UHFFFAOYSA-N 3-bromopyridin-2-amine Chemical compound NC1=NC=CC=C1Br RBCARPJOEUEZLS-UHFFFAOYSA-N 0.000 claims description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 4
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- DOWCWUCBOQRQJE-UHFFFAOYSA-N ditert-butylphosphane;hydrochloride Chemical compound Cl.CC(C)(C)PC(C)(C)C DOWCWUCBOQRQJE-UHFFFAOYSA-N 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 4
- 229960005235 piperonyl butoxide Drugs 0.000 claims description 4
- 125000004591 piperonyl group Chemical group C(C1=CC=2OCOC2C=C1)* 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 2
- CUFDGKBZHJSRDZ-UHFFFAOYSA-N 1-cyclopenta-2,4-dien-1-ylcycloocta-1,5-diene Chemical compound C1(C=CC=C1)C1=CCCC=CCC1 CUFDGKBZHJSRDZ-UHFFFAOYSA-N 0.000 claims description 2
- ZANHUOZJSFYTKD-UHFFFAOYSA-N 2-isocyano-2-methylbutane Chemical compound CCC(C)(C)[N+]#[C-] ZANHUOZJSFYTKD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- XYZMOVWWVXBHDP-UHFFFAOYSA-N cyclohexyl isocyanide Chemical compound [C-]#[N+]C1CCCCC1 XYZMOVWWVXBHDP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- FYRXIYRIBCDWOA-UHFFFAOYSA-N methylidyne-(4-methylphenyl)azanium Chemical compound CC1=CC=C([N+]#C)C=C1 FYRXIYRIBCDWOA-UHFFFAOYSA-N 0.000 claims description 2
- 229960003540 oxyquinoline Drugs 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- PKVRJCUKSNFIBN-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 PKVRJCUKSNFIBN-UHFFFAOYSA-N 0.000 claims description 2
- RCIBIGQXGCBBCT-UHFFFAOYSA-N phenyl isocyanide Chemical compound [C-]#[N+]C1=CC=CC=C1 RCIBIGQXGCBBCT-UHFFFAOYSA-N 0.000 claims description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 2
- FAGLEPBREOXSAC-UHFFFAOYSA-N tert-butyl isocyanide Chemical compound CC(C)(C)[N+]#[C-] FAGLEPBREOXSAC-UHFFFAOYSA-N 0.000 claims description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 2
- 125000004437 phosphorous atom Chemical group 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000012038 nucleophile Substances 0.000 abstract description 2
- 150000004982 aromatic amines Chemical class 0.000 abstract 1
- 150000003003 phosphines Chemical class 0.000 abstract 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon disulfide Substances S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 229910001873 dinitrogen Inorganic materials 0.000 description 15
- 239000007787 solid Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- CKASDXVVKHOJFG-UHFFFAOYSA-N NC(=S)NBr Chemical compound NC(=S)NBr CKASDXVVKHOJFG-UHFFFAOYSA-N 0.000 description 5
- DKDXHNMKTYUOOT-UHFFFAOYSA-N bis(4-bicyclo[2.2.1]heptanyl)phosphane Chemical compound C1CC(C2)CCC12PC1(C2)CCC2CC1 DKDXHNMKTYUOOT-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- YHYGSIBXYYKYFB-UHFFFAOYSA-N octa-2,7-dien-1-ol Chemical compound OCC=CCCCC=C YHYGSIBXYYKYFB-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 3
- 239000012973 diazabicyclooctane Substances 0.000 description 3
- WDOKISJWRVNYNS-UHFFFAOYSA-N dicyclohexylphosphanium;chloride Chemical compound Cl.C1CCCCC1PC1CCCCC1 WDOKISJWRVNYNS-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XMDCYZRDFRTBQH-UHFFFAOYSA-N 3-bromonaphthalen-2-amine Chemical compound C1=CC=C2C=C(Br)C(N)=CC2=C1 XMDCYZRDFRTBQH-UHFFFAOYSA-N 0.000 description 2
- BCNQVNWZDWLQLH-UHFFFAOYSA-N 3-bromothiophen-2-amine Chemical compound NC=1SC=CC=1Br BCNQVNWZDWLQLH-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical class [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical class [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical class PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
- B01J31/2457—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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Abstract
本发明提供一种硫脲型氮膦配体及其制备方法和应用,所述配体的结构式为
Description
技术领域
本发明属于有机化学品合成领域,具体涉及一种硫脲型氮膦配体及其制备方法和应用。
背景技术
2,7-辛二烯-1-醇是一种重要的有机合成中间体,可用来合成高分子材料单体1,9-壬二胺。目前合成2,7-辛二烯-1-醇的方法主要是由1,3-丁二烯经钯催化与水调聚得到。专利JPT2009137843中使用乙酰丙酮钯为催化剂,磺化的苯基膦为配体,在1,3-丁二烯调聚中最高转化率为80.2%,选择性为83.2%;专利GE3925217中使用乙酰丙酮钯为催化剂,三苯基膦为配体,用于1,3-丁二烯与水调聚,总收率为93%。
目前在1,3-丁二烯的调聚反应中,普遍存在着转化率和选择性较低的问题,进而给生产成本带来压力。
发明内容
针对现有技术中存在的不足,本发明的目的在于提供一种硫脲型氮膦配体,用于调聚反应,特别是用于合成2,7-辛二烯-1-醇的调聚反应,采用该配体不但可大大降低金属催化剂的用量,并且转化率、选择性好。
为实现以上发明目的,本发明采用的技术方案如下:
一种硫脲型氮膦配体,所述配体具有如式1所示的结构:
其中,Ar选自苯基、吡啶、噻吩、萘基和胡椒基中的一种或多种,优选苯基;R1选自苯基、降冰片基、环己基、正丁基和叔丁基中的一种或多种,优选降冰片基、叔丁基和苯基中的一种或两种。
所述硫脲型氮膦配体,在钯金属催化剂存在下,形成催化活性体Pd-L,配体与Pd的配位作用使得烯丙基-Pd较难发生β-H消除而形成C8烯烃,同时Pd-L中降冰片基的特殊位阻作用使亲核体对烯丙基-Pd中双键发生亲核进攻时,更倾向于进攻双键端位,具体示意如下式。上述催化剂配位结构使得烷基二烯的转化率和产物2,7-辛二烯-1-醇的选择性大幅提升。
本发明中,所述配体结构为如下结构中的一种或多种:
本发明的另一目的在于提供一种制备所述硫脲型氮膦配体的制备方法。
一种制备硫脲型氮膦配体的制备方法,所述方法包含如下步骤:
S1:2-溴芳胺(I)与CS2生成2-溴芳基异硫氰酸酯(II),并进一步与2-溴芳胺(I)反应完全得到溴代芳基硫脲中间体(III);
S2:硫脲中间体(III)与二取代氯化膦偶联制得硫脲型氮膦配体化合物(IV)。
上述制备步骤的反应式如下:
本发明中,所述S1中2-溴芳胺(I)、溴代芳基硫脲中间体(III)分别具有如式2所示的结构:
其中,Ar选自取代的苯基、吡啶、噻吩、萘基和胡椒基中的一种或多种,优选苯基;优选地,所述2-溴芳胺(I)为2-溴苯胺和/或3-溴-2-氨基吡啶。
本发明中,所述S1中生成2-溴芳基异硫氰酸酯(II)的反应在三乙烯二胺(DABCO)和固体光气(BTC)存在的条件下进行。
本发明中,所述S1中进一步与2-溴芳胺(I)反应在室温搅拌条件下进行。
本发明中,所述S1中所有反应完成后,经正己烷洗涤、干燥得到溴代芳基硫脲中间体(III)。
在一种实施方案中,S1具体为如下工艺:以甲苯为溶剂,在圆底烧瓶中加入1摩尔当量2-溴芳胺I,4摩尔当量三乙烯二胺(DABCO),室温下滴加4摩尔当量二硫化碳(CS2)并反应,至大量白色固体出现,过滤,得白色固体。将白色固体用一定量氯仿溶解,在0℃下滴加1摩尔当量溶于氯仿的固体光气(BTC),滴加完毕加热回流反应,反应结束后,饱和碳酸氢钠淬灭反应,加水萃取,柱层析分离得2-溴芳基异硫氰酸酯(II)。随后加入1摩尔当量2-溴芳胺I,室温反应得固体即为溴代硫脲中间体III。
本发明中,所述S2中二取代氯化膦具有如式3所示的结构:
其中,R1选自苯基、降冰片基、环己基、正丁基和叔丁基中的一种或多种,优选降冰片基、叔丁基和苯基中的一种或两种;优选地,所述二取代氯化膦为二叔丁基氯化膦、二降冰片基氯化膦和二苯基氯化膦中的一种或两种。
在一种实施方案中,S2具体为如下工艺:先将溴代硫脲中间体III在THF中制备为格氏试剂,将所制备的格氏试剂冷却至-78℃,滴加溶于THF的二取代氯化膦,低温下反应1h后室温搅拌12h。反应结束加入饱和硫酸氢钠溶液淬灭反应,萃取有机相并用饱和硫酸氢钠洗涤,浓缩后在乙醇中重结晶得硫脲型氮膦配体化合物(IV)。
本发明的又一目的在于提供一种所述硫脲型氮膦配体的使用方法。
一种硫脲型氮膦配体的使用方法,所述使用方法为:硫脲型氮膦配体与Pd共同催化烷基二烯与水调聚。
在一种实施方式中,所述调聚反应的反应式如下:
本发明中,所述Pd为盐或非盐的形式,价态为Pd(0)或Pd(II);优选所述Pd(0)选自双(叔丁基异腈基)钯、双(叔戊基异腈基)钯、双(环己基异腈基)钯、双(苯基异腈基)钯、双(对甲苯基异腈基)钯、双(2,6-二甲基苯基异腈基)钯、三(二亚苄基丙酮)二钯、(1,5-环辛二烯)(马来酸酐)钯、双(降冰片烯)(马来酸酐)钯、双(马来酸酐)(降冰片烯)钯、(二亚苄基丙酮)(联吡啶基)钯、对苯醌(邻菲罗琳)钯、四(三苯基膦)钯、三(三苯基膦)钯、双(三甲苯基膦)钯和双(三(二甲苯基)膦)钯中的一种或多种;优选所述Pd(II)选择自氯化钯、硝酸钯、醋酸钯、苯甲酸钯、双(乙酰丙酮)钯、双(8-羟基喹啉)钯、双(烯丙基)钯、(环戊二烯基)(1,5-环辛二烯)钯四氟硼酸盐和双(三正丁基膦)钯醋酸盐中的一种或多种;更优选四(三苯基膦)钯、醋酸钯和双(乙酰丙酮)钯中的一种或多种,进一步优选醋酸钯和/或双(乙酰丙酮)钯;优选地,所述Pd催化剂摩尔用量以Pd原子计为50ppm~3000ppm,优选50ppm~200ppm,总量以烷基二烯的摩尔量计。
本发明中,所述硫脲型氮膦配体的用量以P原子计,与Pd原子的摩尔比为(1~10):1,优选(2~5):1。
本发明中,所述水与烷基二烯的摩尔比为(1~5):1,优选(2~3):1。
本发明中,所述反应温度为40~100℃,优选50~70℃;反应压力0.5~2MPaG,优选0.8~1.5MPaG。
本发明的再一目的在于提供一种硫脲型氮膦配体的用途。
一种硫脲型氮膦配体的用途,所述硫脲型氮膦配体用于烷基二烯与水的调聚反应,优选用于1,3-丁二烯与水调聚反应制备2,7-辛二烯-1-醇。
与现有技术相比较,本发明的有益效果为:
(1)本发明的硫脲型氮膦配体,在钯金属催化剂存在下,使得钯在参与催化循环过程中更加高效,产物的转化率大于98.8%。
(2)配体的空间效应使得产物的选择性大于97.6%,有效降低生产成本。
具体实施方式
下面的实施例将对本发明所提供的方法予以进一步的说明,但本发明不限于所列出的实施例,还应包括在本发明所要求的权利范围内其它任何公知的改变。
2-溴芳胺、2-溴异硫氰酸酯、溴代硫脲中间体的转化率通过液相色谱法计算:仪器型号:Agilent 1260,色谱柱:Agilent ZORBAX SB-C18,方法:乙腈/水梯度洗脱,通过面积归一化法计算。
硫脲型氮磷配体的定性表征方法:1H NMR,仪器型号:Bruker 500MHz核磁共振仪。
1,3-丁二烯的转化率、2,7-辛二烯-1-醇的选择性通过气相色谱面积归一化计算:气相色谱仪:Agilent 7890;色谱柱:DB-5;进样口温度:280℃;分流比10:1;H2:Air:N2=40:400:30(mL/min)柱流速5.0mL/min;升温程序:50℃恒温2min,以15℃/min的速度由50℃升温至280℃,280℃恒温5min;FID检测器温度:280℃
试剂信息:
2-溴苯胺(98%)、3-溴-2-氨基吡啶(98%)、3-溴-2-氨基噻吩(98%)、2-氨基-3-溴萘(98%)、二硫化碳(98%)、固体光气(AR)、三乙烯二胺(AR)、二叔丁基氯化膦(AR)、二降冰片基氯化膦(AR)、二苯基氯化膦(AR)、二环己基氯化膦(AR):伊诺凯;
1,3-丁二烯(工业纯):明炬气体。
如未特别说明,其它原料均为普通市售产品,试剂均为分析纯。
实施例1
本实施例反应方程式如下:
(1)往带有搅拌、温度计的反应瓶中加入172.0g 2-溴苯胺(1mol),448.7g三乙烯二胺(DABCO,4mol),加入600ml溶剂甲苯,室温下将304.6g二硫化碳(CS2,4mol)1h内滴加入反应体系中,并继续反应至大量白色固体出现,GC监测2-溴苯胺反应完毕,结束反应,过滤得白色固体。将所得白色固体用400ml氯仿溶解加入带有搅拌、温度计、回流冷凝管的反应瓶中,在0℃下于1h内滴加溶于400ml氯仿的三光气296.8g(BTC,1mol),滴加完毕加热至90℃回流反应5h,反应结束后,100g饱和碳酸氢钠淬灭反应,加水萃取(500mL*3次)、旋蒸浓缩、柱层析分离得2-溴芳基异硫氰酸酯B。
210g 2-溴芳基异硫氰酸酯B(0.98mol)与168.7g 2-溴苯胺(0.98mol)置于带有搅拌、温度计的反应瓶中室温搅拌反应,所得固体经正己烷洗涤(200mL*3次),10kPaA真空干燥即得溴代硫脲C 378.7g。
(2)在带有搅拌、温度计、回流冷凝管、滴液漏斗的反应瓶中将溴代硫脲C 308.9g(0.8mol)在THF中与镁粉反应制备为格氏试剂THF溶液,在-78℃下于30min内滴加205.4g溶于200mol溶剂THF的二降冰片基氯化膦(0.8mol),滴加完毕1h后升至室温反应12h。反应结束后用500ml饱和硫酸氢铵淬灭反应,并使用乙醚洗涤(200mL*3次)、旋蒸浓缩,在300ml乙醇中重结晶得438.8g硫脲型氮磷配体L1,收率82%。
硫脲型氮磷配体L1的核磁氢谱数据为:1H NMR(500MHz,CDCl3):δ=10.00-7.45(m,6H),7.45-7.23(m,2H),7.45-4.81(m,4H),2.89-1.59(m,18H),1.59-0.22(m,24H)。
实施例2
按照实施例1的方法,不同的是,步骤(1)中2-溴苯胺替换为173.01g 3-溴-2-氨基吡啶(1mol),步骤(2)二降冰片基氯化膦替代为144.52g二叔丁基氯化膦(0.8mol)。硫脲型氮磷配体L2,收率79%。
硫脲型氮磷配体L2的核磁氢谱数据为:1H NMR(500MHz,CDCl3):δ=8.25-8.07(m,2H),7.80-7.65(m,2H),6.62-6.45(m,2H),4.05-3.89(m,2H),1.05-0.86(m,36H)。
实施例3
按照实施例1的方法,不同的是,步骤(1)中2-溴苯胺替换为222.09g 2-氨基-3-溴萘(1mol),步骤(2)二降冰片基氯化膦替代为176.51g二苯基氯化膦(0.8mol)。硫脲型氮磷配体L3,收率76%。
硫脲型氮磷配体L3的核磁氢谱数据为:1H NMR(500MHz,CDCl3):δ=9.51(s,1H),9.31(s,1H),7.84-7.63(m,14H),7.51-7.41(m,4H),7.39-7.22(m,12H),6.93(m,2H)。
实施例4
按照实施例1的方法,不同的是,步骤(1)中2-溴苯胺替换为178.05g 2-氨基-3-溴-噻吩(1mol),步骤(2)二降冰片基氯化膦替代为186.18g二环己基氯化膦(0.8mol)。硫脲型氮磷配体L4,收率77%。
硫脲型氮磷配体L4的核磁氢谱数据为:1H NMR(500MHz,CDCl3):δ=9.93(s,2H),6.50-6.40(m,4H),1.30-1.57(m,44H)。
实施例5
在配备有机械搅拌、高纯氮气、温度计的耐压反应釜中加入0.0112g醋酸钯(0.05mmol,50ppm equiv.),0.17g配体L1(0.25mmol,P/Pd=10),水54.0g(3mol,3equiv)和溶剂丙酮500ml,将反应釜用氮气置换3次后,加入液化1,3-丁二烯54.1g(1mol,1equiv),将反应釜升温至65℃并补充氮气至釜内压力1.5MPaG,反应6h,取样GC分析,1,3-丁二烯转化率99.8%,2,7-辛二烯-1-醇选择性98.4%。
实施例6
在配备有机械搅拌、高纯氮气、温度计的耐压反应釜中加入0.0305g双乙酰丙酮钯(0.10mmol,100ppm equiv.),0.13g配体L2(0.25mmol,P/Pd=5),水45.0g(2.5mol,2.5equiv)和溶剂丙酮500ml,将反应釜用氮气置换3次后,加入液化1,3-丁二烯54.1g(1mol,1equiv),将反应釜升温至70℃并补充氮气至釜内压力0.8MPaG,反应8h,取样GC分析,1,3-丁二烯转化率99.3%,2,7-辛二烯-1-醇选择性98.1%。
实施例7
在配备有机械搅拌、高纯氮气、温度计的耐压反应釜中加入0.2319g四三苯基膦钯(0.20mmol,200ppm equiv.),0.2387g配体L3(0.40mmol,P/Pd=4),水36.0g(2.0mol,2equiv)和溶剂丙酮500ml,将反应釜用氮气置换3次后,加入液化1,3-丁二烯54.1g(1mol,1equiv),将反应釜升温至50℃并补充氮气至釜内压力1.2MPaG,反应12h,取样GC分析,1,3-丁二烯转化率98.8%,2,7-辛二烯-1-醇选择性97.6%。
实施例8
在配备有机械搅拌、高纯氮气、温度计的耐压反应釜中加入0.44g氯化钯(2.5mmol,2500ppm equiv.),1.58g配体L4(2.5mmol,P/Pd=2),水90.05g(2.0mol,5equiv)和溶剂丙酮500ml,将反应釜用氮气置换3次后,加入液化1,3-丁二烯54.1g(1mol,1equiv),将反应釜升温至50℃并补充氮气至釜内压力2MPaG,反应9h,取样GC分析,1,3-丁二烯转化率99.1%,2,7-辛二烯-1-醇选择性97.8%。
对比例1
与实施例5比较,不同在于配体L1替换为三苯基膦。
在配备有机械搅拌、高纯氮气、温度计的耐压反应釜中加入0.0112g醋酸钯(0.05mmol,50ppm equiv.),0.07g配体三苯基膦(0.25mmol,P/Pd=10),水54.0g(3mol,3equiv)和溶剂丙酮500ml,将反应釜用氮气置换3次后,加入液化1,3-丁二烯54.1g(1mol,1equiv),将反应釜升温至65℃并补充氮气至釜内压力1.5MPaG,反应6h,取样GC分析,1,3-丁二烯转化率43.6%,2,7-辛二烯-1-醇选择性68.4%。
与对比例1相比,实施例1~3制备的硫脲型氮膦配体用于实施例4~6中1,3-丁二烯调聚制备2,7-辛二烯-1-醇的反应中时,具有1,3-丁二烯转化率高,2,7-辛二烯-1-醇选择性好的优点。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书内容所作的等效变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (10)
3.一种制备权利要求1或2所述硫脲型氮膦配体的制备方法,其特征在于,所述方法包含如下步骤:
S1:2-溴芳胺(I)与CS2生成2-溴芳基异硫氰酸酯(II),并进一步与2-溴芳胺(I)反应完全得到溴代芳基硫脲中间体(III);
S2:硫脲中间体(III)与二取代氯化膦偶联制得硫脲型氮膦配体化合物(IV)。
6.一种硫脲型氮膦配体的使用方法,所述硫脲型氮膦配体为权利要求1或2所述硫脲型氮膦配体或者权利要求3-5中任一项所述制备方法制备的硫脲型氮膦配体,其特征在于,所述使用方法为:硫脲型氮膦配体与Pd共同催化烷基二烯与水调聚。
7.根据权利要求6所述的使用方法,其特征在于,所述Pd为盐或非盐的形式,价态为Pd(0)或Pd(II);优选所述Pd(0)选自双(叔丁基异腈基)钯、双(叔戊基异腈基)钯、双(环己基异腈基)钯、双(苯基异腈基)钯、双(对甲苯基异腈基)钯、双(2,6-二甲基苯基异腈基)钯、三(二亚苄基丙酮)二钯、(1,5-环辛二烯)(马来酸酐)钯、双(降冰片烯)(马来酸酐)钯、双(马来酸酐)(降冰片烯)钯、(二亚苄基丙酮)(联吡啶基)钯、对苯醌(邻菲罗琳)钯、四(三苯基膦)钯、三(三苯基膦)钯、双(三甲苯基膦)钯和双(三(二甲苯基)膦)钯中的一种或多种;优选所述Pd(II)选择自氯化钯、硝酸钯、醋酸钯、苯甲酸钯、双(乙酰丙酮)钯、双(8-羟基喹啉)钯、双(烯丙基)钯、(环戊二烯基)(1,5-环辛二烯)钯四氟硼酸盐和双(三正丁基膦)钯醋酸盐中的一种或多种;更优选四(三苯基膦)钯、醋酸钯和双(乙酰丙酮)钯中的一种或多种,进一步优选醋酸钯和/或双(乙酰丙酮)钯;
优选地,所述Pd催化剂摩尔用量以Pd原子计为50ppm~3000ppm,优选50ppm~200ppm,总量以烷基二烯的摩尔量计。
8.根据权利要求6或7所述的使用方法,其特征在于,所述硫脲型氮膦配体的用量以P原子计,与Pd原子的摩尔比为(1~10):1,优选(2~5):1。
9.根据权利要求6所述的使用方法,其特征在于,所述水与烷基二烯的摩尔比为(1~5):1,优选(2~3):1;
和/或,反应温度为40~100℃,优选50~70℃;反应压力0.5~2MPaG,优选0.8~1.5MPaG。
10.一种硫脲型氮膦配体的用途,所述硫脲型氮膦配体为权利要求1或2所述硫脲型氮膦配体,或权利要求3-5中任一项所述制备方法制备的硫脲型氮膦配体,或权利要求6-9中任一项所述硫脲型氮膦配体的使用方法所使用的硫脲型氮膦配体,其特征在于,所述硫脲型氮膦配体用于烷基二烯与水的调聚反应,优选用于1,3-丁二烯与水调聚反应制备2,7-辛二烯-1-醇。
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