CA2255161C - Preparation of mono- and di-arylphosphines - Google Patents
Preparation of mono- and di-arylphosphines Download PDFInfo
- Publication number
- CA2255161C CA2255161C CA 2255161 CA2255161A CA2255161C CA 2255161 C CA2255161 C CA 2255161C CA 2255161 CA2255161 CA 2255161 CA 2255161 A CA2255161 A CA 2255161A CA 2255161 C CA2255161 C CA 2255161C
- Authority
- CA
- Canada
- Prior art keywords
- process according
- phosphine
- reaction
- psig
- carried out
- 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
- 238000002360 preparation method Methods 0.000 title description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 56
- -1 aryl compound Chemical class 0.000 claims abstract description 29
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 10
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 8
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 claims description 7
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 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 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 150000001412 amines Chemical group 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 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 8
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 150000002940 palladium Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- LFMWZTSOMGDDJU-UHFFFAOYSA-N 1,4-diiodobenzene Chemical compound IC1=CC=C(I)C=C1 LFMWZTSOMGDDJU-UHFFFAOYSA-N 0.000 description 3
- ZLMKEENUYIUKKC-UHFFFAOYSA-N 1-iodo-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(I)=C1 ZLMKEENUYIUKKC-UHFFFAOYSA-N 0.000 description 3
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- IGISPMBUGPHLBY-UHFFFAOYSA-N 1-iodo-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(I)=C1 IGISPMBUGPHLBY-UHFFFAOYSA-N 0.000 description 2
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001502 aryl halides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- DKFDVEXWZZOMGS-UHFFFAOYSA-N (2-phosphanylphenyl)phosphane Chemical compound PC1=CC=CC=C1P DKFDVEXWZZOMGS-UHFFFAOYSA-N 0.000 description 1
- RFXWSCVCWQKXAL-UHFFFAOYSA-N (3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(P)=C1 RFXWSCVCWQKXAL-UHFFFAOYSA-N 0.000 description 1
- FDQGNUSTPULKCR-UHFFFAOYSA-N (4-iodophenyl)phosphane Chemical compound PC1=CC=C(I)C=C1 FDQGNUSTPULKCR-UHFFFAOYSA-N 0.000 description 1
- DXKIVDBWRHJILG-UHFFFAOYSA-N (4-phosphanylphenyl)phosphane Chemical compound PC1=CC=C(P)C=C1 DXKIVDBWRHJILG-UHFFFAOYSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- BBOLNFYSRZVALD-UHFFFAOYSA-N 1,2-diiodobenzene Chemical compound IC1=CC=CC=C1I BBOLNFYSRZVALD-UHFFFAOYSA-N 0.000 description 1
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 1
- JENANTGGBLOTIB-UHFFFAOYSA-N 1,5-diphenylpentan-3-one Chemical compound C=1C=CC=CC=1CCC(=O)CCC1=CC=CC=C1 JENANTGGBLOTIB-UHFFFAOYSA-N 0.000 description 1
- WLPXNBYWDDYJTN-UHFFFAOYSA-N 1-bromo-2,3-dimethylbenzene Chemical class CC1=CC=CC(Br)=C1C WLPXNBYWDDYJTN-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- DANMWBNOPFBJSZ-UHFFFAOYSA-N 1-iodo-2,3-dimethylbenzene Chemical class CC1=CC=CC(I)=C1C DANMWBNOPFBJSZ-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 1
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 1
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical group OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- PZVUZZXBUDKPPH-UHFFFAOYSA-N [3-(trifluoromethyl)phenyl]phosphane Chemical compound FC(F)(F)C1=CC=CC(P)=C1 PZVUZZXBUDKPPH-UHFFFAOYSA-N 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical class BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- GPFIUEZTNRNFGD-UHFFFAOYSA-N bis(3,5-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(PC=2C=C(C)C=C(C)C=2)=C1 GPFIUEZTNRNFGD-UHFFFAOYSA-N 0.000 description 1
- AIYZOGFWAYMZJN-UHFFFAOYSA-N bis(4-iodophenyl)phosphane Chemical compound C1=CC(I)=CC=C1PC1=CC=C(I)C=C1 AIYZOGFWAYMZJN-UHFFFAOYSA-N 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].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 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- SLEAUGLJRCPRES-UHFFFAOYSA-N bis[3-(trifluoromethyl)phenyl]phosphane Chemical compound FC(F)(F)C1=CC=CC(PC=2C=C(C=CC=2)C(F)(F)F)=C1 SLEAUGLJRCPRES-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- XJTQJERLRPWUGL-UHFFFAOYSA-N iodomethylbenzene Chemical class ICC1=CC=CC=C1 XJTQJERLRPWUGL-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- XEWVCDMEDQYCHX-UHFFFAOYSA-N n,n-diethylethanamine;hydron;iodide Chemical compound [I-].CC[NH+](CC)CC XEWVCDMEDQYCHX-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- WXHIJDCHNDBCNY-UHFFFAOYSA-N palladium dihydride Chemical class [PdH2] WXHIJDCHNDBCNY-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- FXXWRINCFWGFCV-UHFFFAOYSA-N tris[3-(trifluoromethyl)phenyl]phosphane Chemical compound FC(F)(F)C1=CC=CC(P(C=2C=C(C=CC=2)C(F)(F)F)C=2C=C(C=CC=2)C(F)(F)F)=C1 FXXWRINCFWGFCV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 125000005023 xylyl group Chemical group 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
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
- C07F9/5072—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure P-H
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Mono- and di-arylphosphines are prepared by reacting an aryl compound that has a leaving group attached to a carbon atom of the aromatic ring with phosphine in the presence of a Group VIII metal catalyst.
Description
The present invention relates to the preparation of mono- and di-arylphosphines.
BACKGROUND OF THE INVENTION
There are known processes to prepare arylphosphines by reacting, for example, phosphorus trichloride with a Grignard reagent or with an organolithium compound, followed by hydrolysis, extraction and distillation. These processes have disadvantages, in that materials used in the processes are expensive, corrosive, difficult to prepare owing particularly to their sensitivity to moisture, and cumbersome to handle on a large scale.
SUMMARY OF THE INVENTION
In one aspect the present invention provides a process for preparing a mono- or d1- arylphosphine, which process comprises reacting an aryl compound bearing a leaving group attached to a carbon atom of the aromatic ring with phosphine in the presence of a Group VIII metal catalyst.
In accordance with the invention it is possible to avoid or alleviate many of the abovementioned disadvantages by reacting phosphine with an aryl compound in the presence of, preferably, a palladium catalyst.
A particular advantage of the present invention is that it is possible to obtain mono-arylphosphines and di-arylphosphines, 1.e., primary and secondary arylphosphines, in good yield, and accompanied by only relatively small amounts of triaryl, 1.e., tertiary phosphine. Owing to the high reactivity of phosphorus compounds, reactions to form arylphosphines usually proceed quickly to the triaryl compound. Consequently, triarylphosphines are available much more readily and cheaply than the corresponding mono- and di-arylphosphines. The mono- and di-arylphosphines are of considerable interest, particularly as intermediates and also as components of catalyst for many reactions. Their possibilities have not been exploited, however, owing to their relative inaccessibility and high price. By means of the present invention, and by careful selection of reaction conditions such as temperature and pressure, it is possible to influence the relative amounts of mono-, d1- and tri-arylphosphines produced.
The aryl compound can have only carbon atoms in the ring, or can be heterocyclic containing one or more nitrogen, oxygen or sulphur atoms. As nitrogen-containing compounds there are mentioned, e.g. pyridine, pyrimidine, piperazine, pyrazole. As an oxygen-containing heterocyclic compound there is mentioned furan. As a sulphur-containing heterocyclic compound there is mentioned thiophene. Examples of hydrocarbyl aryl compounds include phenyl, a-naphthyl, p-naphthyl, biphenyl, phenanthrenyl, anthracenyl, naphthacenyl and 2,2'-bis(1,1'-binaphthyl) groups.
Preferred leaving groups are the halogens, particularly chlorine, bromine and iodine. Other suitable leaving groups include, for example, trifluoromethane-sulfonyloxy, methanesulfonyloxy, toluenesulfonyloxy and trifluoroacetate groups. The leaving group is attached to a carbon atom of the aryl ring. The aryl compound can bear one or more than one leaving group. Examples of aryl groups that bear two leaving groups, and therefore may bear two phosphorus atoms after reaction, include the 1,2-phenyl group, the 1,4-phenyl group, the 2,2'-biphenyl group of formula and the 2,2'-bis(1,1'-binaphthyl) group of formula The aryl halide is preferably an iodo- or a bromo-compound. The aryl moiety can be unsubstituted or can be substituted by groups that do not interfere with the reaction.
Such substituents include hydrocarbyl groups such as alkyl, alkenyl and cycloalkyl groups. Mention is made of alkyl and alkenyl groups, straight chained or branched, having up to about 8 carbon atoms, cycloalkyl groups having from 3 to 8 carbon atoms and aryl groups such as phenyl or naphthyl, aralkyl groups such as benzyl or phenethyl and alkaryl groups such as tolyl or xylyl groups. Other substituents include aryl, acyloxy, alkoxy, alkenoxy and aryloxy groups, again having up to about 8 carbon atoms. Particular compounds include bromotoluenes, bromoxylenes, iodotoluenes and iodoxylenes. The preferred aryl halides are bromobenzene and, especially, iodobenzene.
As stated above, the aryl compound can bear subst ituents that do not part icipate in the react ion with phosphine. It is found that the reaction of the present invention goes better with electron-withdrawing groups, for instance trifluoromethyl, cyano, alkylcarbonyl and alkoxycarbonyl. The substituted compounds that are of greatest interest, however, are those that bear electron-donating groups, for instance lower alkyl and lower alkoxy groups. The aryl compound can bear one, two or more substituents. To avoid steric interference it is preferred that the substituents shall be in the 3-, 4- or 5- position, relative to the leaving group. Mention is made of 3-trifluoromethyl-phenyl, 4-trifluoromethylphenyl, 3-cyanophenyl, 4-cyanophenyl, 3-acetylphenyl, 4-acetylphenyl, 3-methoxycarbonylphenyl, 4-methoxycarbonylphenyl, 3-acetoxyphenyl, 4-acetoxyphenyl, 3-methylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3-methoxyphenyl, 4-methoxyphenyl and 3,5-dimethoxyphenyl groups, and also aryl groups other than phenyl that are correspondingly substituted.
Phosphine is a gas under ambient conditions. The reaction with the aryl compound is preferably carried out under elevated temperature and pressure. The product of the reaction is a mixture of the mono-, d1- and tri-aryl phosphines and the relative ratio of these three products varies, depending upon the temperature and pressure of the reaction, the amount of catalyst and the presence of a base as promoter. The particular reaction conditions selected will therefore depend upon the desired ratio of these products.
Elevated temperature, decreased pressure, a greater amount of catalyst and a greater amount of base promoter all tend to increase the amount of the di-aryl product at the expense of the mono-. Temperatures from 70°C to about 150°C are suitable, preferably from about 90 to 120°C. The pressure may be in the range from ambient to about 600 psig.
The reaction is carried out in the presence of a catalyst that is a metal of Group VIII of the Periodic Table, or a compound of such a metal. Most suitable are the precious metals of Group VIII, of which palladium is preferred.
Mention is made particularly of zero valence compounds of palladium, examples of which include tetrakis(triphenyl-phosphine)palladium, 1,2 bis(diphenylphosphine)ethane palladium, dichlorobis(triphenylphosphine)palladium, 1,3-bis(diphenylphosphine)-propane palladium, 1,4-bis(diphenyl-phosphine)butane palladium and 1,1-bis(diphenylphosphine)-ferrocene palladium.
Mention is made particularly of adducts of a Pd(II) salt and a tertiary phosphine, especially 1:1 adducts as catalysts. As palladium salts there are mentioned the diacetate and the dichloride. The tertiary phosphine can be a 75'365-144 trialkylphosphine, for instance, tri(ethyl)--, tri(propyl)-, tri(n-butyl)-, tri(isobutyl)-, tri(cyclopentyl)-, , tri(cyclohexyl)- and tri(n-octyl)phosphine or a triarylphosphine, of which triphenylphosphine and tri(ortho-tolyl)phosphine are preferred. One preferred catalyst is an adduct of palladium (II) acetate and tris(o-tolyl)phosphine and is described (in German) by Wolfgang A. Herrmarin et al., in Angew. Chem., 1995, Volume 107, pages 1989-1992 and (in English translation) in Angew. Chem. Int. Ed. Engl., 1995, Volume 34, pages 1844-1848.
Mention is made also of palladium compounds that~are standard rr donors, for instance Pd(cyclooctadiene]2, Pd[cyclopentadiene]2 and Pd[dibenzylacetone]2.
The amount of catalyst can range from about 0.05 mole to about 10.0 mole percent, preferably from about 0.1 to about 7.5 mole percent of the aryl compound initially charged..
It is possible to farm the catalyst and then add it to the reaction vessel, or it is possible to add the components of the catalyst, so that the catalyst is formed in situ.
The reaction is preferably carried out in the presence of a solvent. Suitable solvents include glyme, _.
acetonitrile, diethyl ether, anisol.e, di-n-butyl ether, tetrahydrofuran, p-dioxane, toluene, xylene, cumene or a mixture of toluene and isopropanol (e. g. a 3:1 mixture). Also suitable are aliphatic, cycloaliphatic and aromatic hydrocarbons, including hexane, heptane, octane, cyclohexane, benzene and petroleum fractions boiling at 70-140°C. Solvents that have oxidising properties, such as DMSO, should be avoided. Toluene is most preferred.
As stated above the reaction is preferably carried out in the presence of a base promoter such as for example sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, potassium carbonate, sodium ethoxide, potassium ethoxide, ammonium carbonate, ammonium bicarbonate, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide or the like. Organic bases, particularly amines, can also be used.
Mention is made of pyridine and pyridine derivatives and tertiary amines of which triethylamine, tributylamine, and other trialkylamines are preferred.
The phosphine is supplied to a closed reactor under pressure that is suitably in the range of from about 100 psig to 600 psig, preferably about 200 psig to about 500 psig. The temperature of the reactor is elevated to at least about 80°C
but does not usually exceed about 150°C. Preferably the temperature is in the range of from about 100° to about 150°C.
The reaction time may be up to about 6 hours, after which the reaction is quenched. Quenching is suitably carried out by cooling. The reactions between the aryl compound and phosphine do not proceed at reasonable rates much below about 90°C, so cooling the reaction mixture to below about 70 or 80°C is effective. Shorter reaction time and less base both favour the production of mono-arylphosphine over d1- and tri-arylphosphine, so these parameters can be varied in accordance _ 7 _ with the desired product mixture.
The invention is further illustrated in the following examples.
Example 1 Reaction of Iodobenzene with Phosphine at Low Pressure A one litre toluene solution containing iodobenzene (250 g, 1.23 moles), triethylamine (150 g, 1.5 moles) and palladium dimer (1:1 adduct of palladium (II) acetate and trio-tolyl)phosphine, 1.2 g, 1.28 mmole, 0.1 mole $, based on numbers of moles of iodobenzene charged) was charged to a one gallon autoclave under a nitrogen blanket. The solution was maintained at 200 psig phosphine pressure and 100°C, with stirring at 500 rpm, for 5 hours. The autoclave mixture was then cooled to ambient temperature, vented and water (500 ml) was added to dissolve the triethylamine hydriodide salt formed during the reaction. The two liquid phases were discharged from the autoclave and the toluene phase was analysed by GC/FID. This phase was found to be composed of (relative proportions were determined by area percent integration), phenylphosphine (13~), diphenylphosphine (74~) and triphenylphosphine (3~) as well as unreacted iodobenzene (10~) and triethylamine. The total conversion of iodobenzene was approximately 90~. The identity of all of these arylphosphines was unambiguously established by both GC/MS and phosphorus NMR techniques, by comparison with spectra of authentic specimens of these materials.
Both phenylphosphine and diphenylphosphine were _ g _ subsequently isolated in pure form by fractional distillation under vacuum.
Example 2 Reaction of Iodobenzene with Phosphine at High Pressure A one litre xylene solution containing iodobenzene (375 g, 1.84 moles), triethylamine (150 g, 1.5 moles) and the palladium dimer (1:1 adduct of palladium(II) acetate and trio-tolyl)phosphine, 1.20 g, 1.2 mmole, 0.07 mole $) was charged to a one gallon autoclave under a nitrogen blanket.
The solution was maintained at 500 psig phosphine pressure and 110°C, with stirring at 500 rpm, for 5 hours. At this time the autoclave was cooled to ambient temperature, vented and discharged as described above. Analysis of the xylene phase by GC/FID (with area percent integration) gave only monophenylphosphine (9~) and diphenylphosphine (7$), with no sign of triphenyl-phosphine, for a total conversion of iodobenzene of approximately 16~.
Subsequently, the monophenylphosphine present in the mixture was completely converted to diphenylphosphine by maintaining this xylene solution at 100°C for approximately 24 hours under a nitrogen blanket in the absence of phosphine.
Final conversion of diphenylphosphine to the triphenyl-phosphine end product was observed to occur at a significantly faster rate once the monophenylphosphine had been substantially converted to diphenylphosphine.
Example 3 Reaction of 3-Trifluoromethyliodobenzene with Phosphine A one litre toluene solution containing 3-trifluoro-_ g -methyliodobenzene (200 g, 0.73 mole), triethylamine (150 g, 1.5 moles) and palladium dimer (1:1 adduct of palladium (II) acetate and trio-tolyl)phosphine, 0.69 g, 0.73 mmoles, 0.1 mole) was charged to a one gallon autoclave and maintained at 102°C and 200 psig phosphine pressure for 5 hours as described above. A slight exotherm was observed during the first 30 min. of the experiment, which was controlled by means of internal cooling. After isolating it as described above, the organic phase was analysed by GC/FID and GC/MS and found to contain mono (3-trifluoromethylphenyl)phosphine (15~), bis(3-trifluoromethyl-phenyl)phosphine (59~) and tris(3-trifluoro-methylphenyl)-phosphine (5~) in addition to the unreacted 3-trifluoromethyl-iodobenzene (21~).
Example 4 Reaction of 3,5-Dimethyliodobenzene with Phosphine A one litre toluene solution containing 3,5-dimethyliodobenzene (161 g, 0.69 mole), triethylamine (150 g, 1.5 mole) and the palladium dimer (1:1 adduct of palladium (II) acetate and trio-tolyl)phosphine 1.75 g, 1.8 mmole, 0.27 mole) was maintained at 105-110°C and 200 psig phosphine pressure for 10 hours, then cooled, vented and discharged in the usual manner. Analysis of the toluene phase by GC/FID and GC/MS revealed the presence of mono (3,5-dimethylphenyl)-phosphine (14~) and bis(3,5-dimethylphenyl)phosphine (12~) with the remainder being unreacted 3,5-dimethyliodobenzene (74~).
Example 5 Reaction of 1,4-Diiodobenzene with Phosphine A one litre xylene solution of 1,4-diiodobenzene (150 g, 0.50 mole), triethylamine (100 g, 1.0 mole) and the palladium dimer (1:1 adduct of palladium (II) acetate and trio-tolyl)phosphine 0.5 g, 0.5 mmole, 0.1 mole) was maintained at 110°C and 400 psig phosphine pressure for 6 hours, then cooled, vented and discharged in the usual manner.
Analysis of the xylene phase by GC/FID and GC/MS revealed the presence of 4-iodophenylphosphine (17$), bis(4-iodophenyl)phosphine (5~S) and 1,4-bis(phosphino)benzene (1%), with the remainder being unreacted 1,4-diiodobenzene.
Analogously, 1,2-bis(phosphino)benzene can be obtained from 1,2-diiodobenzene.
BACKGROUND OF THE INVENTION
There are known processes to prepare arylphosphines by reacting, for example, phosphorus trichloride with a Grignard reagent or with an organolithium compound, followed by hydrolysis, extraction and distillation. These processes have disadvantages, in that materials used in the processes are expensive, corrosive, difficult to prepare owing particularly to their sensitivity to moisture, and cumbersome to handle on a large scale.
SUMMARY OF THE INVENTION
In one aspect the present invention provides a process for preparing a mono- or d1- arylphosphine, which process comprises reacting an aryl compound bearing a leaving group attached to a carbon atom of the aromatic ring with phosphine in the presence of a Group VIII metal catalyst.
In accordance with the invention it is possible to avoid or alleviate many of the abovementioned disadvantages by reacting phosphine with an aryl compound in the presence of, preferably, a palladium catalyst.
A particular advantage of the present invention is that it is possible to obtain mono-arylphosphines and di-arylphosphines, 1.e., primary and secondary arylphosphines, in good yield, and accompanied by only relatively small amounts of triaryl, 1.e., tertiary phosphine. Owing to the high reactivity of phosphorus compounds, reactions to form arylphosphines usually proceed quickly to the triaryl compound. Consequently, triarylphosphines are available much more readily and cheaply than the corresponding mono- and di-arylphosphines. The mono- and di-arylphosphines are of considerable interest, particularly as intermediates and also as components of catalyst for many reactions. Their possibilities have not been exploited, however, owing to their relative inaccessibility and high price. By means of the present invention, and by careful selection of reaction conditions such as temperature and pressure, it is possible to influence the relative amounts of mono-, d1- and tri-arylphosphines produced.
The aryl compound can have only carbon atoms in the ring, or can be heterocyclic containing one or more nitrogen, oxygen or sulphur atoms. As nitrogen-containing compounds there are mentioned, e.g. pyridine, pyrimidine, piperazine, pyrazole. As an oxygen-containing heterocyclic compound there is mentioned furan. As a sulphur-containing heterocyclic compound there is mentioned thiophene. Examples of hydrocarbyl aryl compounds include phenyl, a-naphthyl, p-naphthyl, biphenyl, phenanthrenyl, anthracenyl, naphthacenyl and 2,2'-bis(1,1'-binaphthyl) groups.
Preferred leaving groups are the halogens, particularly chlorine, bromine and iodine. Other suitable leaving groups include, for example, trifluoromethane-sulfonyloxy, methanesulfonyloxy, toluenesulfonyloxy and trifluoroacetate groups. The leaving group is attached to a carbon atom of the aryl ring. The aryl compound can bear one or more than one leaving group. Examples of aryl groups that bear two leaving groups, and therefore may bear two phosphorus atoms after reaction, include the 1,2-phenyl group, the 1,4-phenyl group, the 2,2'-biphenyl group of formula and the 2,2'-bis(1,1'-binaphthyl) group of formula The aryl halide is preferably an iodo- or a bromo-compound. The aryl moiety can be unsubstituted or can be substituted by groups that do not interfere with the reaction.
Such substituents include hydrocarbyl groups such as alkyl, alkenyl and cycloalkyl groups. Mention is made of alkyl and alkenyl groups, straight chained or branched, having up to about 8 carbon atoms, cycloalkyl groups having from 3 to 8 carbon atoms and aryl groups such as phenyl or naphthyl, aralkyl groups such as benzyl or phenethyl and alkaryl groups such as tolyl or xylyl groups. Other substituents include aryl, acyloxy, alkoxy, alkenoxy and aryloxy groups, again having up to about 8 carbon atoms. Particular compounds include bromotoluenes, bromoxylenes, iodotoluenes and iodoxylenes. The preferred aryl halides are bromobenzene and, especially, iodobenzene.
As stated above, the aryl compound can bear subst ituents that do not part icipate in the react ion with phosphine. It is found that the reaction of the present invention goes better with electron-withdrawing groups, for instance trifluoromethyl, cyano, alkylcarbonyl and alkoxycarbonyl. The substituted compounds that are of greatest interest, however, are those that bear electron-donating groups, for instance lower alkyl and lower alkoxy groups. The aryl compound can bear one, two or more substituents. To avoid steric interference it is preferred that the substituents shall be in the 3-, 4- or 5- position, relative to the leaving group. Mention is made of 3-trifluoromethyl-phenyl, 4-trifluoromethylphenyl, 3-cyanophenyl, 4-cyanophenyl, 3-acetylphenyl, 4-acetylphenyl, 3-methoxycarbonylphenyl, 4-methoxycarbonylphenyl, 3-acetoxyphenyl, 4-acetoxyphenyl, 3-methylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3-methoxyphenyl, 4-methoxyphenyl and 3,5-dimethoxyphenyl groups, and also aryl groups other than phenyl that are correspondingly substituted.
Phosphine is a gas under ambient conditions. The reaction with the aryl compound is preferably carried out under elevated temperature and pressure. The product of the reaction is a mixture of the mono-, d1- and tri-aryl phosphines and the relative ratio of these three products varies, depending upon the temperature and pressure of the reaction, the amount of catalyst and the presence of a base as promoter. The particular reaction conditions selected will therefore depend upon the desired ratio of these products.
Elevated temperature, decreased pressure, a greater amount of catalyst and a greater amount of base promoter all tend to increase the amount of the di-aryl product at the expense of the mono-. Temperatures from 70°C to about 150°C are suitable, preferably from about 90 to 120°C. The pressure may be in the range from ambient to about 600 psig.
The reaction is carried out in the presence of a catalyst that is a metal of Group VIII of the Periodic Table, or a compound of such a metal. Most suitable are the precious metals of Group VIII, of which palladium is preferred.
Mention is made particularly of zero valence compounds of palladium, examples of which include tetrakis(triphenyl-phosphine)palladium, 1,2 bis(diphenylphosphine)ethane palladium, dichlorobis(triphenylphosphine)palladium, 1,3-bis(diphenylphosphine)-propane palladium, 1,4-bis(diphenyl-phosphine)butane palladium and 1,1-bis(diphenylphosphine)-ferrocene palladium.
Mention is made particularly of adducts of a Pd(II) salt and a tertiary phosphine, especially 1:1 adducts as catalysts. As palladium salts there are mentioned the diacetate and the dichloride. The tertiary phosphine can be a 75'365-144 trialkylphosphine, for instance, tri(ethyl)--, tri(propyl)-, tri(n-butyl)-, tri(isobutyl)-, tri(cyclopentyl)-, , tri(cyclohexyl)- and tri(n-octyl)phosphine or a triarylphosphine, of which triphenylphosphine and tri(ortho-tolyl)phosphine are preferred. One preferred catalyst is an adduct of palladium (II) acetate and tris(o-tolyl)phosphine and is described (in German) by Wolfgang A. Herrmarin et al., in Angew. Chem., 1995, Volume 107, pages 1989-1992 and (in English translation) in Angew. Chem. Int. Ed. Engl., 1995, Volume 34, pages 1844-1848.
Mention is made also of palladium compounds that~are standard rr donors, for instance Pd(cyclooctadiene]2, Pd[cyclopentadiene]2 and Pd[dibenzylacetone]2.
The amount of catalyst can range from about 0.05 mole to about 10.0 mole percent, preferably from about 0.1 to about 7.5 mole percent of the aryl compound initially charged..
It is possible to farm the catalyst and then add it to the reaction vessel, or it is possible to add the components of the catalyst, so that the catalyst is formed in situ.
The reaction is preferably carried out in the presence of a solvent. Suitable solvents include glyme, _.
acetonitrile, diethyl ether, anisol.e, di-n-butyl ether, tetrahydrofuran, p-dioxane, toluene, xylene, cumene or a mixture of toluene and isopropanol (e. g. a 3:1 mixture). Also suitable are aliphatic, cycloaliphatic and aromatic hydrocarbons, including hexane, heptane, octane, cyclohexane, benzene and petroleum fractions boiling at 70-140°C. Solvents that have oxidising properties, such as DMSO, should be avoided. Toluene is most preferred.
As stated above the reaction is preferably carried out in the presence of a base promoter such as for example sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, potassium carbonate, sodium ethoxide, potassium ethoxide, ammonium carbonate, ammonium bicarbonate, calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide or the like. Organic bases, particularly amines, can also be used.
Mention is made of pyridine and pyridine derivatives and tertiary amines of which triethylamine, tributylamine, and other trialkylamines are preferred.
The phosphine is supplied to a closed reactor under pressure that is suitably in the range of from about 100 psig to 600 psig, preferably about 200 psig to about 500 psig. The temperature of the reactor is elevated to at least about 80°C
but does not usually exceed about 150°C. Preferably the temperature is in the range of from about 100° to about 150°C.
The reaction time may be up to about 6 hours, after which the reaction is quenched. Quenching is suitably carried out by cooling. The reactions between the aryl compound and phosphine do not proceed at reasonable rates much below about 90°C, so cooling the reaction mixture to below about 70 or 80°C is effective. Shorter reaction time and less base both favour the production of mono-arylphosphine over d1- and tri-arylphosphine, so these parameters can be varied in accordance _ 7 _ with the desired product mixture.
The invention is further illustrated in the following examples.
Example 1 Reaction of Iodobenzene with Phosphine at Low Pressure A one litre toluene solution containing iodobenzene (250 g, 1.23 moles), triethylamine (150 g, 1.5 moles) and palladium dimer (1:1 adduct of palladium (II) acetate and trio-tolyl)phosphine, 1.2 g, 1.28 mmole, 0.1 mole $, based on numbers of moles of iodobenzene charged) was charged to a one gallon autoclave under a nitrogen blanket. The solution was maintained at 200 psig phosphine pressure and 100°C, with stirring at 500 rpm, for 5 hours. The autoclave mixture was then cooled to ambient temperature, vented and water (500 ml) was added to dissolve the triethylamine hydriodide salt formed during the reaction. The two liquid phases were discharged from the autoclave and the toluene phase was analysed by GC/FID. This phase was found to be composed of (relative proportions were determined by area percent integration), phenylphosphine (13~), diphenylphosphine (74~) and triphenylphosphine (3~) as well as unreacted iodobenzene (10~) and triethylamine. The total conversion of iodobenzene was approximately 90~. The identity of all of these arylphosphines was unambiguously established by both GC/MS and phosphorus NMR techniques, by comparison with spectra of authentic specimens of these materials.
Both phenylphosphine and diphenylphosphine were _ g _ subsequently isolated in pure form by fractional distillation under vacuum.
Example 2 Reaction of Iodobenzene with Phosphine at High Pressure A one litre xylene solution containing iodobenzene (375 g, 1.84 moles), triethylamine (150 g, 1.5 moles) and the palladium dimer (1:1 adduct of palladium(II) acetate and trio-tolyl)phosphine, 1.20 g, 1.2 mmole, 0.07 mole $) was charged to a one gallon autoclave under a nitrogen blanket.
The solution was maintained at 500 psig phosphine pressure and 110°C, with stirring at 500 rpm, for 5 hours. At this time the autoclave was cooled to ambient temperature, vented and discharged as described above. Analysis of the xylene phase by GC/FID (with area percent integration) gave only monophenylphosphine (9~) and diphenylphosphine (7$), with no sign of triphenyl-phosphine, for a total conversion of iodobenzene of approximately 16~.
Subsequently, the monophenylphosphine present in the mixture was completely converted to diphenylphosphine by maintaining this xylene solution at 100°C for approximately 24 hours under a nitrogen blanket in the absence of phosphine.
Final conversion of diphenylphosphine to the triphenyl-phosphine end product was observed to occur at a significantly faster rate once the monophenylphosphine had been substantially converted to diphenylphosphine.
Example 3 Reaction of 3-Trifluoromethyliodobenzene with Phosphine A one litre toluene solution containing 3-trifluoro-_ g -methyliodobenzene (200 g, 0.73 mole), triethylamine (150 g, 1.5 moles) and palladium dimer (1:1 adduct of palladium (II) acetate and trio-tolyl)phosphine, 0.69 g, 0.73 mmoles, 0.1 mole) was charged to a one gallon autoclave and maintained at 102°C and 200 psig phosphine pressure for 5 hours as described above. A slight exotherm was observed during the first 30 min. of the experiment, which was controlled by means of internal cooling. After isolating it as described above, the organic phase was analysed by GC/FID and GC/MS and found to contain mono (3-trifluoromethylphenyl)phosphine (15~), bis(3-trifluoromethyl-phenyl)phosphine (59~) and tris(3-trifluoro-methylphenyl)-phosphine (5~) in addition to the unreacted 3-trifluoromethyl-iodobenzene (21~).
Example 4 Reaction of 3,5-Dimethyliodobenzene with Phosphine A one litre toluene solution containing 3,5-dimethyliodobenzene (161 g, 0.69 mole), triethylamine (150 g, 1.5 mole) and the palladium dimer (1:1 adduct of palladium (II) acetate and trio-tolyl)phosphine 1.75 g, 1.8 mmole, 0.27 mole) was maintained at 105-110°C and 200 psig phosphine pressure for 10 hours, then cooled, vented and discharged in the usual manner. Analysis of the toluene phase by GC/FID and GC/MS revealed the presence of mono (3,5-dimethylphenyl)-phosphine (14~) and bis(3,5-dimethylphenyl)phosphine (12~) with the remainder being unreacted 3,5-dimethyliodobenzene (74~).
Example 5 Reaction of 1,4-Diiodobenzene with Phosphine A one litre xylene solution of 1,4-diiodobenzene (150 g, 0.50 mole), triethylamine (100 g, 1.0 mole) and the palladium dimer (1:1 adduct of palladium (II) acetate and trio-tolyl)phosphine 0.5 g, 0.5 mmole, 0.1 mole) was maintained at 110°C and 400 psig phosphine pressure for 6 hours, then cooled, vented and discharged in the usual manner.
Analysis of the xylene phase by GC/FID and GC/MS revealed the presence of 4-iodophenylphosphine (17$), bis(4-iodophenyl)phosphine (5~S) and 1,4-bis(phosphino)benzene (1%), with the remainder being unreacted 1,4-diiodobenzene.
Analogously, 1,2-bis(phosphino)benzene can be obtained from 1,2-diiodobenzene.
Claims (26)
1. A process for preparing mono- and di-arylphosphines which comprises reacting an aryl compound bearing a leaving group attached to a carbon atom of the aromatic ring with phosphine in the presence of a Group VIII
metal catalyst.
metal catalyst.
2. A process according to claim 1, wherein the reaction is carried out in the presence of a base promoter.
3. A process according to claim 2, wherein the base promoter is selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, sodium ethoxide, potassium ethoxide, ammonium carbonate, ammonium bicarbonate, calcium oxide, calcium hydroxide, magnesium oxide, and magnesium hydroxide.
4. A process according to claim 2, wherein the base promoter is an amine.
5. A process according to claim 4, wherein the amine is pyridine or a pyridine derivative.
6. A process according to claim 4, wherein the amine is a tertiary amine.
7. A process according to claim 6, wherein the tertiary amine is triethylamine.
8. A process according to any one of claims 2 to 7, wherein the base promoter is present in molar excess of up to 2-fold relative to the aryl compound.
9. A process according to any one of claims 1 to 8, wherein the reaction is carried out at a pressure from about ambient to about 600 psig.
10. A process according to claim 9, wherein the pressure is in a range from about 100 psig to about 600 psig.
11. A process according to claim 10, wherein the pressure is in a range from about 200 psig to about 600 psig.
12. A process according to any one of claims 1 to 11, wherein the reaction is carried out at a temperature in the range from ambient temperature to 120°C.
13. A process according to any one of claims 1 to 11, wherein the reaction is carried out at a temperature in the range from 70°C to 150°C.
14. A process according to claim 13, wherein the temperature is in the range from 90°C to 120°C.
15. A process according to any one of claims 1 to 14, wherein the catalyst is an adduct of a palladium (II) compound and a triaryl phosphine.
16. A process according to claim 15, wherein the catalyst is a 1:1 adduct of palladium (II) acetate and tri(orthotolyl)phosphine.
17. A process according to any one of claims 1 to 16, wherein the leaving group is a halogen.
18. A process according to claim 17, wherein the leaving group is iodine.
19. A process according to any one of claims 1 to 18, wherein the aryl compound bearing the leaving group is iodobenzene.
20. A process according to any one of claims 1 to 18, wherein the aryl compound bears as a substituent one, two or more electron-withdrawing groups.
21. A process according to claim 20, wherein the electron-withdrawing group is selected from the group consisting of trifluoromethyl, cyano, acetyl, methoxycarbonyl, and acetoxy.
22. A process according to any one of claims 1 to 18, wherein the aryl compound bears as a substituent one, two or more methyl or methoxy groups.
23. A process according to any one of claims 20 to 22, wherein the substituent is in the 3-, 4- or 5- position relative to the leaving group.
24. A process according to any one of claims 1 to 23, wherein the reaction is carried out in the presence of a solvent.
25. A process according to claim 24, wherein the solvent is toluene.
26. A process according to claim 24, wherein the solvent is xylene.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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CA 2255161 CA2255161C (en) | 1998-12-03 | 1998-12-03 | Preparation of mono- and di-arylphosphines |
EP99951952A EP1140950A1 (en) | 1998-12-03 | 1999-10-12 | Preparation of mono- and di-arylphosphines |
PCT/US1999/023777 WO2000032613A1 (en) | 1998-12-03 | 1999-10-12 | Preparation of mono- and di-arylphosphines |
US09/856,754 US6563005B1 (en) | 1998-12-03 | 1999-10-12 | Preparation of mono- and di-arylphosphines |
AU64278/99A AU6427899A (en) | 1998-12-03 | 1999-10-12 | Preparation of mono- and di-arylphosphines |
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CA 2255161 CA2255161C (en) | 1998-12-03 | 1998-12-03 | Preparation of mono- and di-arylphosphines |
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CA2255161A1 CA2255161A1 (en) | 2000-06-03 |
CA2255161C true CA2255161C (en) | 2003-09-16 |
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CA 2255161 Expired - Fee Related CA2255161C (en) | 1998-12-03 | 1998-12-03 | Preparation of mono- and di-arylphosphines |
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EP (1) | EP1140950A1 (en) |
AU (1) | AU6427899A (en) |
CA (1) | CA2255161C (en) |
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CA2310353A1 (en) * | 2000-05-31 | 2001-11-30 | Cytec Technology Corp. | Synthesis of diphosphinoarenes |
CA2310355A1 (en) * | 2000-05-31 | 2001-11-30 | John H. Hillhouse | Phosphorus aromatic compounds and polymers thereof |
DE102006013936A1 (en) | 2006-03-16 | 2007-09-20 | Valeo Schalter Und Sensoren Gmbh | Method for operating an environment recognition system of a vehicle, in particular a proximity detection or parking assistance system and associated system |
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US5399771A (en) * | 1994-06-01 | 1995-03-21 | Merck & Co., Inc. | Process of synthesizing binaphthyl derivatives |
CA2144907A1 (en) * | 1995-03-17 | 1996-09-18 | John H. Hillhouse | Preparation of arylalkyl phosphines, phopphine oxides and sulfides |
-
1998
- 1998-12-03 CA CA 2255161 patent/CA2255161C/en not_active Expired - Fee Related
-
1999
- 1999-10-12 AU AU64278/99A patent/AU6427899A/en not_active Abandoned
- 1999-10-12 WO PCT/US1999/023777 patent/WO2000032613A1/en not_active Application Discontinuation
- 1999-10-12 EP EP99951952A patent/EP1140950A1/en not_active Withdrawn
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WO2000032613A1 (en) | 2000-06-08 |
EP1140950A1 (en) | 2001-10-10 |
CA2255161A1 (en) | 2000-06-03 |
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