WO2014023549A1 - Method for producing amines by homogeneously-catalyzed alcohol amination in the presence of a complex catalyst, which contains iridium and an amino acid - Google Patents
Method for producing amines by homogeneously-catalyzed alcohol amination in the presence of a complex catalyst, which contains iridium and an amino acid Download PDFInfo
- Publication number
- WO2014023549A1 WO2014023549A1 PCT/EP2013/065202 EP2013065202W WO2014023549A1 WO 2014023549 A1 WO2014023549 A1 WO 2014023549A1 EP 2013065202 W EP2013065202 W EP 2013065202W WO 2014023549 A1 WO2014023549 A1 WO 2014023549A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alcohol
- amine
- group
- primary
- complex catalyst
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 150000001413 amino acids Chemical class 0.000 title claims abstract description 36
- 150000001412 amines Chemical class 0.000 title claims abstract description 23
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 14
- 238000005576 amination reaction Methods 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 68
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 150000001298 alcohols Chemical class 0.000 claims abstract description 19
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- -1 methonine Chemical compound 0.000 claims description 25
- 150000003512 tertiary amines Chemical class 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
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- 239000001257 hydrogen Substances 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 239000002585 base Substances 0.000 claims description 13
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 13
- 125000004122 cyclic group Chemical group 0.000 claims description 12
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
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- 150000001356 alkyl thiols Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- KFVUXNKQQOUCAH-UHFFFAOYSA-N butan-1-ol;propan-2-ol Chemical compound CC(C)O.CCCCO KFVUXNKQQOUCAH-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 125000004623 carbolinyl group Chemical group 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical group C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000004852 dihydrofuranyl group Chemical group O1C(CC=C1)* 0.000 description 1
- 125000005043 dihydropyranyl group Chemical group O1C(CCC=C1)* 0.000 description 1
- 125000005057 dihydrothienyl group Chemical group S1C(CC=C1)* 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- VPNOHCYAOXWMAR-UHFFFAOYSA-N docosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCN VPNOHCYAOXWMAR-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- KAJZYANLDWUIES-UHFFFAOYSA-N heptadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCN KAJZYANLDWUIES-UHFFFAOYSA-N 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- 125000005241 heteroarylamino group Chemical group 0.000 description 1
- 125000005553 heteroaryloxy group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- PQPVPZTVJLXQAS-UHFFFAOYSA-N hydroxy-methyl-phenylsilicon Chemical class C[Si](O)C1=CC=CC=C1 PQPVPZTVJLXQAS-UHFFFAOYSA-N 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- OOXRAGYSSZWMAE-UHFFFAOYSA-N icosa-5,8,11,14-tetraen-1-amine Chemical compound CCCCCC=CCC=CCC=CCC=CCCCCN OOXRAGYSSZWMAE-UHFFFAOYSA-N 0.000 description 1
- NYBCZSBDKXGAGM-UHFFFAOYSA-N icosa-5,8,11,14-tetraen-1-ol Chemical compound CCCCCC=CCC=CCC=CCC=CCCCCO NYBCZSBDKXGAGM-UHFFFAOYSA-N 0.000 description 1
- BUHXFUSLEBPCEB-UHFFFAOYSA-N icosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCN BUHXFUSLEBPCEB-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 1
- 229960000367 inositol Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 125000005644 linolenyl group Chemical group 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229950006780 n-acetylglucosamine Drugs 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PZFYOFFTIYJCEW-UHFFFAOYSA-N n-tridecyltridecan-1-amine Chemical compound CCCCCCCCCCCCCNCCCCCCCCCCCCC PZFYOFFTIYJCEW-UHFFFAOYSA-N 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- INAMEDPXUAWNKL-UHFFFAOYSA-N nonadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCN INAMEDPXUAWNKL-UHFFFAOYSA-N 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- GJVFBWCTGUSGDD-UHFFFAOYSA-L pentamethonium bromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCC[N+](C)(C)C GJVFBWCTGUSGDD-UHFFFAOYSA-L 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 125000003198 secondary alcohol group Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000003507 tetrahydrothiofenyl group Chemical group 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000004627 thianthrenyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3SC12)* 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 125000004568 thiomorpholinyl group Chemical group 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- PYGHKJQHDXSHES-UHFFFAOYSA-N undec-10-en-1-amine Chemical compound NCCCCCCCCCC=C PYGHKJQHDXSHES-UHFFFAOYSA-N 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 150000003738 xylenes Chemical class 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
Definitions
- the present invention relates to a process for the preparation of amines (A) by homogeneously catalyzed alcoholamination of alcohols (AI) with an amination agent (Am) with dehydration.
- Preferred amines (A) which can be prepared by the process according to the invention are secondary or tertiary amines.
- Secondary amines (As) have at least one secondary amino group (> NH).
- Tertiary amines (At) have at least one tertiary amino group (> N-).
- Amines (A) are valuable products with a multitude of different uses, for example as solvents or stabilizers, for the synthesis of chelate formers, as starting materials for the production of synthetic resins, inhibitors, surface-active substances, as intermediates in the preparation of fuel additives, surfactants, medicaments. and crop protection agents, curing agents for epoxy resins, catalysts for polyurethanes, as intermediates for the preparation of quaternary ammonium compounds, plasticizers, corrosion inhibitors, synthetic resins, ion exchangers, textile auxiliaries, dyes, vulcanization accelerators and / or emulsifiers.
- the preparation of secondary and tertiary amines is described, for example, in K. Fujita, Z. Li, N.
- a disadvantage of the processes described above is that the use of bases such as K 2 C0 3 or NaHC0 3 is absolutely necessary.
- the bases used must be separated in an additional process step. Temperatures well above 100 ° C are required to achieve acceptable yields. This makes the processes described above energy-consuming and also unsuitable for thermally labile reactants.
- the object is achieved by a process for the preparation of amines (A) by Chrysleraminierung of alcohols (AI) with an amination agent (Am) with elimination of water, wherein the alcohol lamination is carried out in the presence of a complex catalyst containing iridium and an amino acid.
- alcohols (AI) and aminating agents (Am) are used as starting materials.
- Suitable alcohols are compounds which contain at least one hydroxyl group (hereinafter also referred to as OH group).
- the OH group may be present in the form of a primary alcohol group (-CH 2 -OH) or in the form of a secondary alcohol group (> CH-OH).
- alcohols (AI) are preferred which have at least one primary alcohol group.
- Alcohols (Al) are virtually all known alcohols which fulfill the abovementioned requirements.
- the alcohols can be straight-chain, branched or cyclic.
- the alcohols may also bear substituents which are inert under the alcohol alcoholation reaction conditions, for example, alkyloxy, alkenyloxy, dialkylamino and halogens (F, Cl, Br, I).
- Alcohols (Al) used are preferably monoalcohols, diols, triols or polyols.
- Mono alcohols have an OH group.
- Diols have two OH groups.
- Triols have three OH groups.
- Polyols have more than three OH groups.
- Suitable alcohols (AI) are, for example, those of the general formula (XX):
- R and R are independently selected from the group consisting of
- the ring system is preferably selected from the group consisting of unsubstituted or at least mono-substituted C 5 -C 0 cycloalkyl, C 5 - Ci 0 -Heterocyclyl, C 5 -C 4 -Aryl and C 5 -C 4 -Heteroaryl, wherein the substituents have the meanings given above.
- Particularly preferred ring systems are selected from the group consisting of unsubstituted or at least monosubstituted cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, anthryl and phenanthryl.
- Suitable examples are the following monoalcohols: methanol, ethanol, n-propanol, isopropanol n-butanol, 2-butanol, isobutanol, n-pentanol, ethanolamine (monoethanolamine), 2-ethylhexanol, cyclohexanol, benzyl alcohol, 2-phenyl-ethanol , 2- (p-Methoxyphenyl) ethanol, furfuryl alcohol, 2- (3,4-dimethoxyphenyl) ethanol, hydroxymethylfurfural, lactic acid, serine and fatty alcohols such as 1-heptanol (önanthalcohol; C 7 H 16 O), 1-octanol (capryl alcohol; C 8 H 18 0), 1 -Nonanol (pelargonyl C 9 H 2 oO), 1-decanol (capric alcohol; C 1 0H 22 O), 1 -Undecanol (C11 H24O
- Particularly preferred monoalcohols are selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, ethanolamine, 1-heptanol (eananthalcohol; C 7 H 16 O), 1-octanol (capryl alcohol, C 8 H 18 0), 1 - nonanol (pelargonic C 9 H 2 oO), 1 - decanol (capric alcohol; C 1 0H 22 O), 1 -Undecanol (Cn H 24 0), 10-undecene-1-ol (C 11 H 22 O), 1 - dodecanol (lauryl alcohol; Ci 2 H 26 0), 1 -Tridecanol (C 3 H 28 0), 1 -Tetradecanol (myristyl alcohol, C 4 H 30 O), 1 -Pentadecanol (C 5 H 32 0), 1 -Hexadecanol ( cetyl alcohol; C 6 H 34 0),
- the abovementioned fatty alcohols include both the pure compounds and mixtures of isomers of the primary fatty alcohols.
- Ethanolamine can be used both as alcohol (AI) and as aminating agent (Am).
- diols which can be used as starting materials in the process according to the invention are 1, 4-butanediol (1, 4-butylene glycol), 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8 -Oktandiol, 1, 9-nonanediol, 9-cis-octadecene-1, 12-diol (ricinol; Ci 8 H 36 02), 2,4-dimethyl-2,5-hexanediol, Hydroxypivalin- klareneopentylglykolester, diethylene glycol, triethylene glycol, 1,4-Bis (2-hydroxyethyl) piperazine, diisopropanolamine, N-butyldiethanolamine, 1,10-decanediol, 1,12-do
- triols or polyols which have at least one functional group of the formula (-CH 2 -OH) or (> CH-OH).
- triols or polyols which can be used as starting materials in the process according to the invention are glycerol, trimethylolpropane, triisopropanolamine, triethanolamine, polyvinyl alcohol, polyalkylene glycols whose OH groups can be either primary and / or secondary alcohols, 2,2-bis ( hydroxymethyl) -1,3-propanediol (pentaerythritol), sorbitol, inositol, carbohydrates, sugars, sugar alcohols and polymers: such as glucose, mannose, fructose, ribose, deoxyribose, galactose, N-acetyl-glucosamine, fucose, rhamnose, sucrose , Lactose, cellobiose, maltose and
- aminating agent virtually all known amines can be used which have at least one primary or secondary amino group.
- Primary amines suitable as aminating agent (Am) are, for example, those of the general formula (XXI):
- (XXI), in the , 30 is selected from the group consisting of unsubstituted or at least monosubstituted CrC 3 o-alkyl, C 5 -Ci 0 -cycloalkyl, C 5 -Ci 0 - heterocyclyl, C 5 -C 4 -aryl and C 5 -C 4 -heteroaryl wherein the substituents are selected from the group consisting of F, Cl, Br, OH, OR 22 , CN, NH 2 , NHR 22 , N (R 22 ) 2 , COOH, COOR 22 , C (0) NH 2 , C (0) NHR 22, C (0) N (R 22) 2, d-do-alkyl, C 5 -C 0 cycloalkyl, C 5 -C 0 - heterocyclyl, C 5 -C 4 aryl and C 5 - Ci 4 -heteroaryl, wherein R is selected from CrCl 0 alkyl
- Suitable aminating agents (Am) are, for example, the following primary amines: methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, butan-2-amine, isobutylamine, tert-butylamine, n-pentylamine, n-hexylamine , 2-ethylhexylamine, aniline, cyclohexylamine, benzylamine, 2-phenylethylamine, 1-adamantylamine, 2-adamantylamine and fatty amines such as 1-heptanamine, 1-octanamine, 1 -nonanamine, 1-decanamine, 1-undecanamine, 10-undecene-1 -amine, 1-dodecanamine, 1-tridecanamine, 1-tetradecanamine, 1-pentadecanamine, 1-hexadecanamine, 1-heptadecanamine, 1-octadecanamine, 9
- aminating agent (Am) particularly preferred primary amines are selected from the group consisting of monomethylamine, 1-ethylamine, 1-propylamine, isopropylamine, aniline, ethanolamine and tert-butylamine.
- Secondary amines suitable as aminating agent (Am) are, for example, those of the general formula (XXII):
- R and R are independently selected from the group consisting of unsubstituted or at least mono-substituted -C 3 -alkyl, C 5 -C 0 cycloalkyl, C5-C10 heterocyclyl, C 5 -C 4 aryl and C 5 -C 4 - Heteroaryl or R 31 and R 32 together with the nitrogen atom to which they are attached form a five- to administratzehengliedriges unsubstituted or at least monosubstituted ring system, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, OR 22nd , CN, NH 2 , NHR 22 , N (R 22 ) 2 , COOH, COOR 22 , C (0) NH 2 , C (O) NHR 22 , C (O) N (R 22 ) 2 , C Ci 0 - alkyl, C 5 -C 0 cycloalkyl, C 5 -C 0
- R 22 is selected from CrCl 0 alkyl and C 5 -C 0 aryl.
- the ring system is preferably selected from the group consisting of unsubstituted or at least monosubstituted pyrrolidinyl, pyrrolyl, piperidinyl, wherein the substituents are as above have mentioned meanings.
- Examples of secondary amines suitable as aminating agent (Am) are dimethylamine, diethylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, dihexylamine, ditridecylamine, di (2-ethylhexyl) amines, methylethylamine, piperidine, pyrrolidine, morpholine, N -Methylaniline, dibenzylamine, tetrahydroquinoline.
- Particularly preferred secondary amines are selected from the group consisting of dimethylamine and dibutylamine.
- At least one complex catalyst which contains iridium as metal component and at least one amino acid as ligand.
- the complex catalyst contains an ⁇ -amino acid as a ligand.
- the inventive method is preferably carried out homogeneously catalyzed.
- the process according to the invention is carried out homogeneously catalysed in the presence of a complex catalyst of the general formula (I):
- R 1 and R 2 are independently hydrogen, unsubstituted or at least mono-substituted d-Cio-alkyl, C 5 -C 0 cycloalkyl, C 5 - are Cio-heterocyclyl, C 5 -C 0 aryl or C 5 -C -heteroaryl 0 or
- R 1 and R 2 together with the atoms to which they are attached form an unsubstituted or at least monosubstituted five to ten membered ring system, wherein the substituents are selected from the group consisting of NR 8 R 9 , OR 10 , SR 11 , C (0 ) oR 12, C (0) NR 13 R 14, NHC (NH 2) 2 + and unsubstituted or at least mono-substituted C 5 -C 0 aryl and C 5 -C 0 heteroaryl, wherein the substituents are selected from OH and NH 2 ;
- X is fluoride, chloride, bromide or iodide
- R 3 , R 4 , R 5 , R 6 and R 7 are independently hydrogen, methyl, ethyl, n-propyl, iso-propyl or phenyl;
- R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are independently hydrogen or C
- the complex catalyst may be neutral, single or double positively charged.
- the complex catalyst is neutral.
- the substituent NHC (NH 2 ) 2 + herein represents a substituent of the structural formula below, wherein the substituent is bonded via the dashed bond.
- Particularly preferred are complex catalysts (I) in which R 3 , R 4 , R 5 , R 6 and R 7 are methyl and X is chloride.
- the complex catalyst of general formula (I) has a stereogenic center on the iridium central atom.
- the general formula (I) includes according to the invention all stereoisomers (represented by the wavy bonds in formula (I)) and is not limited to the configuration shown in formula (I).
- the formula (I) thus also includes the stereoisomers (Iaa) and (Ibb).
- the complex catalyst (I) also comprises all stereoisomers.
- the complex catalyst (I) also includes derivatives obtainable from the complex catalyst by protonation or deprotonation.
- the complex catalysts (I) used according to the invention can be prepared from an iridium-containing catalyst precursor by reaction with an amino acid in the presence of a solvent and a base.
- suitable iridium-containing catalyst precursors are [Cp * IrF 2 ] 2, [Cp * IrCI 2 ] 2, [Cp * IrBr 2 ] 2, [Cp * Ir 2 ] 2, with [Cp * IrCl 2 ] 2 being preferred.
- Aprotic polar solvents are suitable as solvents for the preparation of the complex catalyst according to the invention, with acetonitrile being particularly preferred.
- As the base alkali or alkaline earth metal carbonates are suitable, with potassium carbonate (K 2 C0 3 ) is preferred.
- the reaction is preferably carried out under a protective gas atmosphere, such as nitrogen or argon.
- the reaction temperature is generally 0 to 100 ° C, preferably 10 to 40 ° C and particularly preferably 15 to 25 ° C.
- the preparation of the complex catalyst (I) is preferably carried out at normal pressure, that is to say the ambient pressure.
- the amino acid used as the ligand is preferably used in equimolar amounts relative to the iridium contained in the iridium-containing catalyst precursor.
- the reaction time is in the range of 5 minutes to 100 hours, preferably in the range of 5 to 50 hours, preferably in the range of 15 to 30 hours.
- the base used preferably potassium carbonate
- the solvent preferably acetonitrile
- amino acids As amino acids, ⁇ -amino acids are preferred.
- the amino acids can be used both as L-a-amino acid and as D-a-amino acid.
- D-L- ⁇ -amino acids it is possible to use mixtures of the aforementioned configuration isomers, so-called D-L- ⁇ -amino acids.
- amino acids both naturally occurring amino acids and exclusively synthetically accessible amino acids can be used.
- Preferred amino acids are selected from the group consisting of alanine, valine, leucine, iso-leucine, proline, tryptophan, phenylalanine, methonine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartate, glutamate, lysine, arginine, histidine , Citrulline, homocysteine, homoserine, (4R) -4-hydroxy-proline, (5R) -5-hydroxy-lysine, ornithine and sarcosine.
- the abovementioned amino acids can be used both as La amino acids and as Da amino acids.
- amino acids are selected from the group consisting of glycine, valine, proline and sarcosine.
- Particularly preferred amino acids are selected from the group consisting of proline and sarcosine.
- an amino acid selected from the group consisting of alanine, valine, leucine, iso-leucine, proline , Tryptophan, phenylalanine, methonine, glycine, serine,
- complex catalysts (I) containing iridium as a metal component, Cp * (1, 2,3,4,5-pentamethylcyclopentadienyl anion), chloride and an amino acid selected from the group consisting of glycine, valine, proline and sarcosine.
- branched, unbranched, saturated and unsaturated groups are understood as meaning CrC 30 or C 1 -C 10 -alkyl or C 1 -C 6 -alkyl. Preference is given to alkyl groups having 1 to 6 carbon atoms (C 1 -C 6 -alkyl). More preferred are alkyl groups having 1 to 4 carbon atoms (C 1 -C 4 alkyl).
- saturated alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl and hexyl.
- Examples of unsaturated alkyl groups are vinyl, allyl, butenyl, ethynyl and propynyl.
- the CrCio-alkyl group may be unsubstituted or substituted with one or more substituents selected from the group F, Cl, Br, hydroxy (OH), d-Cio-alkoxy, C 5 - Cio-aryloxy, C 5 -Cio-alkylaryloxy, C 5 -C 0 heteroaryloxy containing at least one heteroatom selected from N, O, S, oxo, C 0 -C 3 cycloalkyl, phenyl, C 5 -C 0 heteroaryl containing at least one heteroatom selected from N, O, S, C 5 -Ci 0 -Heterocyclyl containing at least one heteroatom selected from N, O, S, naphthyl, amino, C is Cio-alkylamino, C 5 -
- C 5 -C 0 cycloalkyl saturated, unsaturated monocyclic and polycyclic groups are understood herein.
- Examples of C 5 -C 0 cycloalkyl are cyclopentyl, cyclohexyl or cycloheptyl.
- the cycloalkyl groups may be unsubstituted or substituted with one or more substituents as defined above for the group Ci-Cio-alkyl.
- aryl or C 5 -C 0 is aryl meant an aromatic ring system having 5 to 14 or 5 to 10 carbons under C 5 -C.
- the aromatic ring system may be monocyclic or bicyclic.
- aryl groups are phenyl, naphthyl, such as 1-naphthyl and 2-naphthyl.
- the aryl group may be unsubstituted or substituted with one or more substituents as defined above under Ci-Ci 0 -alkyl.
- C 5 -C 4 -heteroaryl or C5-C1 0 - heteroaryl understood a heteroaromatic system containing at least one hetero atom selected from the group N, O, and S.
- the heteroaryl groups may be monocyclic or bicyclic.
- nitrogen is a ring atom
- the present invention also includes N-oxides of the nitrogen-containing heteroaryls.
- heteroaryls are thienyl, benzothienyl, 1-naphthothienyl, thianthrenyl, furyl, benzofuryl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, isoindolyl, indazolyl, purinyl, isoquinolinyl, quinolinyl, acridinyl, naphthyridinyl, quinoxalinyl, Quinazolinyl, cinnolinyl, piperidinyl, carbolinyl, thiazolyl, oxazolyl, isothiazolyl, isoxazolyl.
- the heteroaryl groups may be unsubstituted or substituted with one or more substituents which have been defined above under Ci-Ci 0 -alkyl.
- ring systems In the context of the present invention will be five- to ten-membered ring systems that contain at least one heteroatom from the group N, O and S in C 5 -C 0 heterocyclyl.
- the ring systems can be monocyclic or bicyclic.
- suitable heterocyclic ring systems are piperidinyl, pyrrolidinyl, pyrrolinyl, pyrazolinyl, pyrazolidinyl, morpholinyl, thiomorpholinyl, pyranyl, thiopyranyl, piperazinyl, indolinyl, dihydrofuranyl, tetrahydrofuranyl, dihydrothiophenyl, tetrahydrothiophenyl, dihydropyranyl and tetrahydropyranyl.
- the complex catalyst (I) according to the invention is preferably used directly in its active form.
- the complex catalyst is prepared, as described above, in a process step upstream of the actual alcohol lamination.
- the alcohol lamination is preferably carried out homogeneously catalyzed.
- homogeneous catalysis is understood to mean that the catalytically active part of the complex catalyst (I) is at least partially dissolved in the liquid reaction medium.
- at least 90% of the complex catalyst used in the process is dissolved in the liquid reaction medium, more preferably at least 95%, most preferably more than 99%, most preferably the complex catalyst is completely dissolved in liquid reaction medium before (100%), respectively based on the total amount in the liquid reaction medium.
- the complex catalyst is used in amounts ranging from 0.01 to 20 mol%, preferably in the range of 0.1 to 10 mol%, and more preferably in the range of 0.2 to 6 mol% per mol of OH group in the starting material of Alcohol lamination is included.
- the reaction takes place in the liquid phase generally at a temperature of 20 to 250 ° C.
- the process according to the invention is preferably carried out at temperatures in the range from 50 ° C. to 150 ° C., more preferably in the range from 50 to 130 ° C. and in particular in the range from 70 to 99 ° C.
- the liquid phase may be derived from the starting materials, i. the alcohol (AI) or the aminating agent (Am) and / or a solvent are formed.
- the reaction can generally be carried out at a total pressure of 1 to 100 bar absolute, which may be both the autogenous pressure of the solvent at the reaction temperature and the pressure of a gas such as nitrogen, argon or hydrogen.
- the process according to the invention is preferably carried out at a total pressure in the range from 1 to 30 bar absolute, more preferably at a total pressure in the range from 1 to 5 bar absolute.
- the process according to the invention is carried out in the absence of hydrogen. In the absence of hydrogen is understood according to the invention that the reaction no additional hydrogen is supplied. Optionally traces of hydrogen supplied via other gases and traces of hydrogen formed in the reaction are considered to be in the absence of hydrogen according to the present invention.
- the average reaction time is generally 15 minutes to 100 hours, preferably 5 hours to 30 hours.
- the aminating agent (Am) may be used in stoichiometric, substoichiometric or superstoichiometric amounts with respect to the hydroxyl groups to be aminated in the alcohol (AI).
- the aminating agent (Am) is preferably used in stoichiometric amounts.
- the process according to the invention can be carried out both in the presence of a solvent and without solvent.
- the process according to the invention is preferably carried out in the presence of a solvent.
- Suitable solvents are polar and nonpolar solvents which can be used in pure form or in mixtures. For example, only a non-polar or only one polar solvent can be used in the process according to the invention. It is also possible to use mixtures of two or more polar solvents or mixtures of two or more non-polar solvents or mixtures of one or more polar with one or more non-polar solvents.
- nonpolar solvents are saturated and unsaturated hydrocarbons, such as hexane, heptane, octane, cyclohexane, benzene, toluene, xylene (o-xylene, m-xylene, p-xylene) and mesitylene, and linear and cyclic ethers, such as diethyl ether, 1 4-dioxane, MTBE (tert-butyl methyl ether), diglyme and 1,2-dimethoxyethane.
- toluene xylenes or mesitylene. Particularly preferred is toluene.
- Suitable polar solvents are water, dimethylformamide, formamide, tert-amyl alcohol and acetonitrile. Preferably, water is used. Water can be added both prior to the reaction, formed in the reaction as water of reaction or added after the reaction in addition to the water of reaction.
- bases can have a positive effect on product formation.
- Suitable bases include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides, alkaline earth metal alkoxides, alkali metal carbonates, alkaline earth carbonates, alkali metal bicarbonates and alkaline earth hydrogen carbonates, of which 0.01 to 100 molar equivalents can be used with respect to the metal catalyst used.
- the use of bases is not absolutely necessary in the process according to the invention. In a preferred embodiment, the process according to the invention is carried out without the addition of the abovementioned bases.
- the aminating agent (Am), the alcohol, preferably together with a solvent, and the complex catalyst (I) are introduced into a reactor.
- the supply of the aminating agent (Am), the alcohol (AI), the solvent and the complex catalyst (I) can be carried out simultaneously or separately.
- the reaction can be carried out continuously, in semibatch mode, in batch mode, back-mixed in product as a solvent or not backmixed in a straight pass.
- At least one primary or secondary hydroxyl group of the alcohol (AI) is reacted with the amino group of the aminating agent (Am) to form a secondary or tertiary amine, each forming one mole of water of reaction per mole of hydroxyl group reacted.
- Secondary amines are obtained when a primary or secondary monoalcohol is used as the alcohol (AI) and a primary amine is used as the aminating agent (Am).
- the alcohol (AI) used is preferably a primary alcohol (R 20 or R 21 in formula (XX) is hydrogen).
- the formation of secondary amines is exemplified by the following reaction equation (1).
- the present invention thus also provides a process for the preparation of secondary amines (As) by alcoholamination of alcohols (AI), in which Alcohol is a primary or secondary monoalcohol and as aminating agent (Am) a primary amine is used.
- AI alcoholamination of alcohols
- Am aminating agent
- Another object of the present invention is a process in which a primary or secondary monoalcohol is used as the alcohol (AI) and a primary amine is used as the aminating agent (Am) and a secondary amine (As) is obtained as the amine (A).
- Tertiary amines (At) are obtained when a primary or secondary monoalcohol is used as the alcohol (AI) and a secondary amine is used as the aminating agent (Am).
- the alcohol (AI) used is preferably a primary alcohol.
- the formation of tertiary amines is exemplified by the following reaction equation (2).
- the present invention thus also provides a process for the preparation of tertiary amines (At), by Chrysleraminierung of alcohols (AI), in which a primary or secondary monoalcohol is used as alcohol and as aminating agent (Am) a secondary amine.
- Another object of the present invention is a process in which a primary or secondary monoalcohol is used as the alcohol (AI) and a secondary amine is used as the aminating agent (Am), and a tertiary amine (At) is obtained as the amine (A).
- Tertiary amines (At) can moreover be obtained if the alcohol (AI) used is a primary or secondary monoalcohol in excess, preferably at least twice, and as aminating agent (Am) a primary amine.
- the alcohol (AI) used is preferably a primary alcohol.
- the formation of tertiary amines (At) is exemplified by the following reaction equation (3).
- the present invention thus also provides a process for the preparation of tertiary amines (At), by Chrysleraminierung of alcohols (AI), in which as alcohol a primary or secondary monoalcohol in excess, preferably at least twice, and as aminating agent (Am) is a primary amine is used.
- a further subject of the present invention is a process in which the alcohol (AI) used is a primary or secondary monoalcohol in excess, preferably at least twice, and as aminating agent (Am) a secondary amine and as amine (A) a tertiary amine ( At).
- tertiary amines (At) can be obtained when the alcohol (Al) used is a diol having primary or secondary hydroxyl groups and as aminating agent (Am) a primary amine.
- the alcohol (Al) used is preferably a diol (XXa) which contains two primary hydroxyl groups.
- the formation of tertiary amines is exemplified by the following reaction equation (4).
- Unsubstituted or at least monosubstituted bivalent radicals are understood as meaning "unsubstituted bivalent radicals" selected from the group consisting of ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene and octamethylene
- the present invention thus also provides a process for the preparation of tertiary amines (At) by alcoholamination of alcohols (Al), in which a diol having two primary hydroxyl groups is used as alcohol and a primary amine is used as aminating agent (Am).
- a further subject of the present invention is a process in which the alcohol (AI) is a diol having two primary hydroxyl groups and the aminating agent (Am) is a primary amine and the amine (A) is a tertiary amine (At).
- the reaction effluent resulting from the reaction generally contains the corresponding amination product (i.e., a secondary or tertiary amine), optionally the solvent, the complex catalyst (I), optionally unreacted starting materials, and the resulting water of reaction.
- amination product i.e., a secondary or tertiary amine
- solvent i.e., a solvent
- complex catalyst (I) optionally unreacted starting materials
- the suspension was filtered through Celite and the filter cake was washed several times with dichloromethane (total amount 50 ml).
- the combined yellow filtrates were concentrated to a volume of 5 ml and overlaid with an excess of dry pentane (30 ml).
- the solvent mixture was decanted and the crystals were washed with dry pentane.
- the complex catalyst (I) thus obtained was dried under vacuum to obtain a yellow or orange solid.
- the formation of the complex catalyst is represented by the following reaction equation (5)
- Elemental analysis calc. C 37.61%, H 5.26%, N 2.92%; gef. 37.05%, H 5.40%, N 2.88%.
- Elemental analysis calc. C 34.62%, H 4.69%, N 3.1 1%; gef. C 33.50%, H 4.50%, N 2.92%.
- Elemental analysis calc. C 37.77%, H 4.86%, N 2.94%; gef. C 38.52%, H 5.15%, N 2.83%.
- the crude product was extracted with dichloromethane (2 x 10 ml). The combined organic phases were washed with a saturated sodium bicarbonate solution and a saturated saline solution and dried over sodium sulfate (Na 2 S0 4 ). After filtration, the solvent was distilled under vacuum and the resulting product of the alcohol lamination was purified by column chromatography on Florisil (magnesium silicate) with a 30: 1 to 10: 1 mixture of dichloromethane and methanol. After removal of the solvent, a colorless liquid was obtained. The reaction follows the reaction equation (6) (non-stoichiometric representation).
- Example 15 in Table 1 When using one amino acid (glycine, see Example 13 in Table 1), no conversion was observed. In Example 15 in Table 1, the reaction was carried out in the presence of [Cp * IrCI 2 ] 2 at 95 ° C. In this case, only very low conversion of the starting materials and unsatisfactory selectivity with respect to the target product N-hexyloctylamine (3) were achieved.
- the intermediate (3a) could be detected. With a 6-hour reaction time, sales between 34 and 90% were achieved.
- the selectivity for the target product (3) ranged from 79 to 90%.
- the desired target products (18 to 22) were obtained in good yields.
- the formation of / V-dialkylated aniline derivatives was not observed.
- the reaction was carried out here at 100 ° C.
- the secondary amines (As) were obtained in yields of> 90%.
- Analyzes of the reaction mixtures by GC-MS were performed on an Agilent 19091 S-433 modular GC with a split-mode capillary injection system and a flame ionization detector.
- a standard HP-5 capillary column (Agilent 19091 S-433, 5% phenylmethylsiloxane, capillary 30 m ⁇ 250 ⁇ ⁇ 0.25 m) was used (flow helium 1 .0 mL / min, temperature program: initial 50 ° C for 2 min, 10 ° C / min to 280 ° C, 280 ° C for 2 min).
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Abstract
The invention relates to a method for producing amines (A) by the alcohol amination of alcohols (Al) using an amination agent (Am), water being separated in the process, wherein the alcohol amination is carried out in the presence of a complex catalyst, which contains iridium and an amino acid.
Description
Verfahren zur Herstellung von Aminen durch homogen-katalysierte Alkoholaminierung in Gegenwart eines Komplexkatalysators, der Iridium und eine Aminosäure enthält Process for the preparation of amines by homogeneously catalyzed alcohol lamination in the presence of a complex catalyst containing iridium and an amino acid
Beschreibung description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Aminen (A) durch homogen-katalysierte Alkoholaminierung von Alkoholen (AI) mit einem Aminierungsmittel (Am) unter Wasserabspaltung. Bevorzugte Amine (A), die nach dem erfindungsgemäßen Verfahren hergestellt werden können, sind sekundäre oder tertiäre Amine. Sekundäre Amine (As) weisen mindestens eine sekundäre Aminogruppe (>NH) auf. Tertiäre Amine (At) weisen mindestens eine tertiäre Aminogruppe (>N-) auf. Amine (A) sind wertvolle Produkte mit einer Vielzahl unterschiedlicher Verwendungen, beispielsweise als Lösungsmittel oder Stabilisatoren, zur Synthese von Chelat- Bildnern, als Edukte zur Herstellung von Kunstharzen, Inhibitoren, grenzflächenaktiven Substanzen, als Zwischenprodukte bei der Herstellung von Kraftstoffadditiven, Tensiden, Arznei- und Pflanzenschutzmitteln, Härtern für Epoxidharze, Katalysatoren für Polyurethane, als Zwischenprodukte zur Herstellung quaternärer Ammoniumverbindungen, Weichmachern, Korrosionsinhibitoren, Kunstharzen, lonentauschern, Textilhilfsmitteln, Farbstoffen, Vulkanisationsbeschleunigern und/oder Emulgatoren. Die Herstellung von sekundären und tertiären Aminen ist beispielsweise in K. Fujita, Z. Li, N. Ozeki, R. Yamaguchi, Tetrahedron Lett. 2003, 44, 2687-2690 und K. Fujita, Y. Enoki, R. Yamaguchi, Tetrahedron 2008, 64, 1943-1954 beschrieben. Bei den dort beschriebenen Verfahren wird als Katalysator [Cp*lrCI2]2 in Gegenwart einer Base wie K2C03 oder NaHC03 und Toluol als Lösungsmittel verwendet. Als Edukte zur Herstellung der sekundären oder tertiären Amine können primäre oder sekundäre Alkohole eingesetzt werden. Als Aminkomponenten werden primäre oder sekundäre Aminedukte eingesetzt, wobei primäre Aminedukte zu sekundären Aminen und sekundäre Aminedukte zu tertiären Aminen führen. Nachteilig an den vorstehend beschriebenen Verfahren ist, dass der Einsatz von Basen wie K2C03 oder NaHC03 zwingend erforderlich ist. Die eingesetzten Basen müssen in einem zusätzlichen Verfahrensschritt abgetrennt werden. Zur Erzielung akzeptabler Ausbeuten sind zudem Temperaturen von deutlich über 100 °C erforderlich. Dies macht die vorstehend beschriebenen Verfahren energieaufwändig und zudem für thermisch labile Edukte ungeeignet. The present invention relates to a process for the preparation of amines (A) by homogeneously catalyzed alcoholamination of alcohols (AI) with an amination agent (Am) with dehydration. Preferred amines (A) which can be prepared by the process according to the invention are secondary or tertiary amines. Secondary amines (As) have at least one secondary amino group (> NH). Tertiary amines (At) have at least one tertiary amino group (> N-). Amines (A) are valuable products with a multitude of different uses, for example as solvents or stabilizers, for the synthesis of chelate formers, as starting materials for the production of synthetic resins, inhibitors, surface-active substances, as intermediates in the preparation of fuel additives, surfactants, medicaments. and crop protection agents, curing agents for epoxy resins, catalysts for polyurethanes, as intermediates for the preparation of quaternary ammonium compounds, plasticizers, corrosion inhibitors, synthetic resins, ion exchangers, textile auxiliaries, dyes, vulcanization accelerators and / or emulsifiers. The preparation of secondary and tertiary amines is described, for example, in K. Fujita, Z. Li, N. Ozeki, R. Yamaguchi, Tetrahedron Lett. 2003, 44, 2687-2690 and K. Fujita, Y. Enoki, R. Yamaguchi, Tetrahedron 2008, 64, 1943-1954. In the methods described therein [* LRCI 2 Cp] 2 is used in the presence of a base such as K 2 C0 3 or NaHC0 3 and toluene as a solvent as a catalyst. As starting materials for the preparation of secondary or tertiary amines primary or secondary alcohols can be used. The amine components used are primary or secondary amine starting materials, primary amine starting materials leading to secondary amines and secondary amine starting materials to tertiary amines. A disadvantage of the processes described above is that the use of bases such as K 2 C0 3 or NaHC0 3 is absolutely necessary. The bases used must be separated in an additional process step. Temperatures well above 100 ° C are required to achieve acceptable yields. This makes the processes described above energy-consuming and also unsuitable for thermally labile reactants.
O. Saidi, A. J. Blacker, M. M. Farah, S. P. Marsden, J. M. J. Williams Chem. Commun.O. Saidi, A.J. Blacker, M.M. Farah, S.P. Marsden, J.M.J. Williams Chem. Commun.
2010, 46, 1541 -1543 und R. Kawahara, K. Fujita, R. Yamaguchi, Adv. Synth. Catal.2010, 46, 1541-1543 and R. Kawahara, K. Fujita, R. Yamaguchi, Adv. Synth. Catal.
201 1 , 353, 1 161 -1 168 beschreiben Verfahren zur Herstellung von sekundären oder
tertiären Aminen. Als Katalysatoren werden dabei [Cp*lrl2]2 beziehungsweise [Cp*lr(NH3)3][X]2 eingesetzt, wobei„X" Cl, Br oder I bedeutet. Hierbei werden primäre oder sekundäre Alkohole mit primären oder sekundären Aminedukten umgesetzt. Die Umsetzung wird dabei in Wasser durchgeführt, wobei der Einsatz einer Base nicht zwingend erforderlich ist. Nachteilig an diesen Verfahren ist, dass zur Erreichung akzeptabler Ausbeuten ebenfalls Temperaturen von deutlich über 100 °C erforderlich sind. Somit sind auch diese Verfahren energieaufwändig und für die Umsetzung thermisch labiler Edukte nur bedingt geeignet. Obwohl im Stand der Technik die homogen-katalysierte Herstellung sekundärer und tertiärer Amine beschrieben ist, besteht dennoch ein großer Bedarf an alternativen Verfahren, die, auch bei Temperaturen unter 100 °C, gute Aktivitäten und Selektivitäten aufweisen. Aufgabe der vorliegenden Erfindung ist es somit, ein Verfahren zur Herstellung von Aminen, insbesondere sekundären oder tertiären Aminen, bereitzustellen, das die Amine in guten Ausbeuten und Selektivitäten liefert, und bei dem die Bildung von unerwünschten Nebenprodukten weitestgehend vermieden wird. Darüber hinaus soll das Verfahren auch bei niedrigen Temperaturen durchführbar sein, bevorzugt bei Temperaturen, die unterhalb der Temperaturen der im Stand der Technik beschriebenen Verfahren liegen. 201 1, 353, 1 161 -1 168 describe processes for the preparation of secondary or tertiary amines. [Cp * lrl 2 ] 2 or [Cp * lr (NH 3 ) 3 ] [X] 2 are used here as catalysts, where "X" denotes Cl, Br or I. Here, primary or secondary alcohols are reacted with primary or secondary amine initiators The reaction is carried out in water, whereby the use of a base is not absolutely necessary.A disadvantage of this method is that to achieve acceptable yields also temperatures of well above 100 ° C are required.Thus, these methods are energy consuming and for Although the state of the art describes the homogeneously catalyzed preparation of secondary and tertiary amines, there is nevertheless a great need for alternative processes which, even at temperatures below 100 ° C., have good activities and selectivities It is therefore an object of the present invention to provide a process for the preparation of amines, in particular secondary ones or tertiary amines, which provides the amines in good yields and selectivities, and in which the formation of undesirable by-products is largely avoided. In addition, the process should also be feasible at low temperatures, preferably at temperatures which are below the temperatures of the processes described in the prior art.
Gelöst wird die Aufgabe durch ein Verfahren zur Herstellung von Aminen (A) durch Alkoholaminierung von Alkoholen (AI) mit einem Aminierungsmittel (Am) unter Wasserabspaltung, wobei die Alkoholaminierung in Gegenwart eines Komplexkatalysators durchgeführt wird, der Iridium und eine Aminosäure enthält. The object is achieved by a process for the preparation of amines (A) by Alkoholaminierung of alcohols (AI) with an amination agent (Am) with elimination of water, wherein the alcohol lamination is carried out in the presence of a complex catalyst containing iridium and an amino acid.
Überraschend wurde festgestellt, dass mit den im erfindungsgemäßen Verfahren eingesetzten Komplexkatalysatoren, die Iridium und eine Aminosäure enthalten, sekundär oder tertiäre Amine gegenüber den im Stand der Technik beschriebenen Verfahren teilweise in deutlich verbesserten Ausbeuten und Selektivitäten erhalten werden. Der im erfindungsgemäßen Verfahren eingesetzte Komplexkatalysator ermöglicht darüber hinaus die Herstellung von sekundären oder tertiären Aminen bei, gegenüber den im Stand der Technik beschriebenen Verfahren, niedrigeren Temperaturen. Darüber hinaus ist der Einsatz von Basen im erfindungsgemäßen Verfahren nicht zwingend erforderlich. Surprisingly, it has been found that with the complex catalysts used in the process according to the invention, which contain iridium and an amino acid, secondary or tertiary amines are obtained in some cases in significantly improved yields and selectivities over the processes described in the prior art. The complex catalyst used in the process according to the invention also allows the preparation of secondary or tertiary amines at, compared to the methods described in the prior art, lower temperatures. In addition, the use of bases in the process according to the invention is not absolutely necessary.
Bei der homogen-katalysierten Alkoholaminierung werden die Hydroxylgruppen (-OH) des eingesetzten Alkohols (AI) mit der Aminogruppe des eingesetzten Aminierungsmittels (Am) zu einer sekundären (>NH) oder tertiären Aminogruppe (>N-)
umgesetzt, wobei je umgesetzter Hydroxylgruppe ein Molekül Wasser entsteht. Als Aminierungsmittel (Am) können primäre oder sekundäre Amine eingesetzt werden. In the homogeneous-catalyzed Alkoholaminierung the hydroxyl groups (-OH) of the alcohol used (AI) with the amino group of the aminating agent used (Am) to a secondary (> NH) or tertiary amino group (> N-) implemented, wherein each reacted hydroxyl group, a molecule of water. As aminating agent (Am) primary or secondary amines can be used.
Edukte reactants
Im erfindungsgemäßen Verfahren werden Alkohole (AI) und Aminierungsmittel (Am) als Edukte eingesetzt. In the process according to the invention, alcohols (AI) and aminating agents (Am) are used as starting materials.
Als Alkohole (AI) sind Verbindungen geeignet, die mindestens eine Hydroxylgruppe (nachfolgend auch als OH-Gruppe bezeichnet) enthalten. Die OH-Gruppe kann dabei in Form einer primären Alkoholgruppe (-CH2-OH) oder in Form einer sekundären Alkoholgruppe (>CH-OH) vorliegen. Als Edukte sind Alkohole (AI) bevorzugt, die mindestens eine primäre Alkoholgruppe aufweisen. Als Alkohole (AI) sind praktisch alle bekannten Alkohole geeignet, die die vorstehend genannten Voraussetzungen erfüllen. Die Alkohole können geradkettig, verzweigt oder zyklisch sein. Die Alkohole können darüber hinaus Substituenten tragen, die sich unter den Reaktionsbedingungen der Alkoholaminierung inert verhalten, beispielsweise Alkyloxy, Alkenyloxy, Dialkylamino und Halogene (F, Cl, Br, I). Als Alkohole (AI) werden bevorzugt Monoalkohole, Diole, Triole oder Polyole eingesetzt. Monoalkohole weisen eine OH-Gruppe auf. Diole weisen zwei OH-Gruppen auf. Triole weisen drei OH- Gruppen auf. Polyole weisen mehr als drei OH-Gruppen auf. Suitable alcohols (AI) are compounds which contain at least one hydroxyl group (hereinafter also referred to as OH group). The OH group may be present in the form of a primary alcohol group (-CH 2 -OH) or in the form of a secondary alcohol group (> CH-OH). As starting materials, alcohols (AI) are preferred which have at least one primary alcohol group. Alcohols (Al) are virtually all known alcohols which fulfill the abovementioned requirements. The alcohols can be straight-chain, branched or cyclic. The alcohols may also bear substituents which are inert under the alcohol alcoholation reaction conditions, for example, alkyloxy, alkenyloxy, dialkylamino and halogens (F, Cl, Br, I). Alcohols (Al) used are preferably monoalcohols, diols, triols or polyols. Mono alcohols have an OH group. Diols have two OH groups. Triols have three OH groups. Polyols have more than three OH groups.
Geeignete Alkohole (AI) sind beispielsweise solche der allgemeinen Formel (XX): Suitable alcohols (AI) are, for example, those of the general formula (XX):
R20— CH OH R 20 - CH OH
R21 R 21
(XX) (XX)
in der in the
R und R unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus R and R are independently selected from the group consisting of
Wasserstoff, unsubstituiertem oder zumindest monosubstituiertem CrC30-Hydrogen, unsubstituted or at least monosubstituted CrC 30 -
Alkyl, C5-Ci0-Cycloalkyl, C5-Ci0-Heterocyclyl, C5-Ci4-Aryl und C5-Ci4- Heteroaryl oder R20 und R21 zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, ein fünf- bis vierzehngliedriges unsubstituiertes oder zumindest monosubstituiertes Ringsystem ausbilden, wobei die Substituenten ausgewählt sind aus der Gruppe bestehend aus F, Cl, Br, OH, OR22, CN, NH2, NHR22, N(R22)2, COOH, COOR22, C(0)NH2,
C(0)NHR22, C(0)N(R22)2, d-do-Alkyl, C5-Ci0-Cycloalkyl, C5-Ci0- Heterocyclyl, C5-Ci4-Aryl und C5-Ci4-Heteroaryl, wobei R22 ausgewählt ist aus CrCi0-Alkyl und C5-Ci0-Aryl. Alkyl, C 5 -C 0 cycloalkyl, C 5 -C 0 heterocyclyl, C 5 -C 4 aryl and C 5 -C 4 - heteroaryl, or R 20 and R 21 together with the carbon atom to which they are attached, form a five- to fourteen-membered unsubstituted or at least monosubstituted ring system, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, OR 22 , CN, NH 2 , NHR 22 , N (R 22 ) 2 , COOH, COOR 22 , C (0) NH 2 , C (0) NHR 22, C (0) N (R 22) 2, d-do-alkyl, C 5 -C 0 cycloalkyl, C 5 -C 0 - heterocyclyl, C 5 -C 4 aryl and C 5 -C 4 -heteroaryl, wherein R 22 is selected from CrCl 0 alkyl and C 5 -C 0 aryl.
Für den Fall, dass R20 und R21 zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, ein Ringsystem ausbilden, ist das Ringsystem bevorzugt ausgewählt aus der Gruppe bestehend aus unsubstituiertem oder zumindest monosubstituiertem C5-Ci0-Cycloalkyl, C5-Ci0-Heterocyclyl, C5-Ci4-Aryl und C5-Ci4-Heteroaryl, wobei die Substituenten die vorstehend genannten Bedeutungen aufweisen. For the case that R 20 and R 21, form together with the carbon atom to which they are attached form a ring system, the ring system is preferably selected from the group consisting of unsubstituted or at least mono-substituted C 5 -C 0 cycloalkyl, C 5 - Ci 0 -Heterocyclyl, C 5 -C 4 -Aryl and C 5 -C 4 -Heteroaryl, wherein the substituents have the meanings given above.
Besonders bevorzugte Ringsysteme sind ausgewählt aus der Gruppe bestehend aus unsubstituiertem oder zumindest monosubstituiertem Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooktyl, Phenyl, Naphtyl, Anthryl und Phenanthryl. Particularly preferred ring systems are selected from the group consisting of unsubstituted or at least monosubstituted cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, anthryl and phenanthryl.
Geeignet sind beispielsweise die folgenden Monoalkohole: Methanol, Ethanol, n- Propanol, Isopropanol n-Butanol, 2-Butanol, iso-Butanol, n-Pentanol, Ethanolamin (Monoethanolamin), 2-Ethylhexanol, Cyclohexanol, Benzylalkohol, 2-Phenyl-ethanol, 2- (p-Methoxyphenyl)ethanol, Furfurylalkohol, 2-(3,4-Dimethoxyphenyl)ethanol, Hydroxymethylfurfural, Milchsäure, Serin und Fettalkohole wie 1 -Heptanol (önanthalkohol; C7H160), 1 -Octanol (Caprylalkohol; C8H180), 1 -Nonanol (Pelargonalkohol; C9H2oO), 1 -Decanol (Caprinalkohol; C10H22O), 1 -Undecanol (C11 H24O), 10-Undecen-1 -ol (C11H22O), 1 -Dodecanol (Laurylalkohol; Ci2H260), 1 - Tridecanol (C13H28O), 1 -Tetradecanol (Myristylalkohol; Ci4H30O), 1 -Pentadecanol (C15H32O), 1 -Hexadecanol (Cetylalkohol; Ci6H340), 1 Heptadecanol (Ci7H360), 1 - Octadecanol (Stearylalkohol; Ci8H380), 9-cis-Octadecen-1 -ol (Oleylalkohol; Ci8H360), 9-trans-Octadecen-1 -ol (Erucylalkohol; Ci8H360), all-cis-9,12-Octadecadien-1 -ol (Linoleylalkohol; Ci8H340), all-cis-9,12,15-Octadecatrien-1 -ol (Linolenylalkohol; Ci8H320), 1 -Nonadecanol (C19H40O), 1 -Eicosanol (Arachidylalkohol; C20H42O), 9-cis- Eicosen-1 -ol (Gadoleylalkohol; C2oH400), 5,8,1 1 ,14-Eicosatetraen-1 -ol (C2oH340), 1 - Heneicosanol (C21 H44O), 1 -Docosanol (Behenylalkohol; C22H46O), 1 -3cis-Docosen-1 -ol (Erucylalkohol; C22H44O) und 1 -3trans-Docosen-1 -ol (Brassidylalkohol; C22H44O). Suitable examples are the following monoalcohols: methanol, ethanol, n-propanol, isopropanol n-butanol, 2-butanol, isobutanol, n-pentanol, ethanolamine (monoethanolamine), 2-ethylhexanol, cyclohexanol, benzyl alcohol, 2-phenyl-ethanol , 2- (p-Methoxyphenyl) ethanol, furfuryl alcohol, 2- (3,4-dimethoxyphenyl) ethanol, hydroxymethylfurfural, lactic acid, serine and fatty alcohols such as 1-heptanol (önanthalcohol; C 7 H 16 O), 1-octanol (capryl alcohol; C 8 H 18 0), 1 -Nonanol (pelargonyl C 9 H 2 oO), 1-decanol (capric alcohol; C 1 0H 22 O), 1 -Undecanol (C11 H24O), 10-undecene-1-ol (C11H22O ), 1 -Dodecanol (lauryl alcohol; Ci 2 H 26 0), 1 - tridecanol (C1 3 H2 O 8), 1 -Tetradecanol (myristyl alcohol, C 4 H 30 O), 1 -Pentadecanol (C1 5 3 H 2O), 1 -Hexadecanol (cetyl alcohol; C 6 H 34 0), 1 heptadecanol (C 7 H 36 0), 1 - octadecanol (stearyl alcohol; Ci 8 H 38 0), 9-cis-octadecene-1-ol (oleyl alcohol; Ci 8 H 36 0), 9-trans-octadecene-1-ol (erucyl alcohol; Ci 8 H 36 O), all-cis-9,12-octadeca dien-1-ol (linoleyl alcohol; C 8 H 34 0), all-cis-9,12,15-octadecatrien-1-ol (linolenyl; Ci 8 H 32 0), 1 -Nonadecanol (C1 H4 0 9 O), 1 -Eicosanol (arachidyl alcohol; C2 0 H42O), 9-cis-eicosen-1-ol (gadoleyl alcohol, C 2 oH 40 0), 5,8,1 1, 14-eicosatetraene-1-ol (C 2 oH 34 0), 1-heneicosanol (C21 H44O), 1-docosanol (behenyl alcohol; C22H4 6 O), 1-cis-docosen-1-ol (erucyl alcohol; C22H44O) and 1 -3 trans-docosen-1-ol (brassidyl alcohol; C22H44O).
Besonders bevorzugte Monoalkohole sind ausgewählt aus der Gruppe bestehend aus Methanol, Ethanol, n-Propanol, Isopropanol, Ethanolamin, 1 -Heptanol (Önanthalkohol; C7H160), 1 -Octanol (Caprylalkohol; C8H180), 1 -Nonanol (Pelargonalkohol; C9H2oO), 1 - Decanol (Caprinalkohol; C10H22O), 1 -Undecanol (CnH240), 10-Undecen-1 -ol (C11H22O), 1 -Dodecanol (Laurylalkohol; Ci2H260), 1 -Tridecanol (Ci3H280), 1 -Tetradecanol (Myristylalkohol; Ci4H30O), 1 -Pentadecanol (Ci5H320), 1 -Hexadecanol (Cetylalkohol; Ci6H340), 1 Heptadecanol (Ci7H360), 1 -Octadecanol (Stearylalkohol; Ci8H380), 9-cis- Octadecen-1 -ol (Oleylalkohol; Ci8H360), 9-trans-Octadecen-1 -ol (Erucylalkohol;
CisHseO), all-cis-9,12-Octadecadien-1 -ol (Linoleylalkohol; Ci8H340), all-cis-9,12,15- Octadecatrien-1 -ol (Linolenylalkohol; Ci8H320) und 1 -Nonadecanol (Ci9H40O). Particularly preferred monoalcohols are selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, ethanolamine, 1-heptanol (eananthalcohol; C 7 H 16 O), 1-octanol (capryl alcohol, C 8 H 18 0), 1 - nonanol (pelargonic C 9 H 2 oO), 1 - decanol (capric alcohol; C 1 0H 22 O), 1 -Undecanol (Cn H 24 0), 10-undecene-1-ol (C 11 H 22 O), 1 - dodecanol (lauryl alcohol; Ci 2 H 26 0), 1 -Tridecanol (C 3 H 28 0), 1 -Tetradecanol (myristyl alcohol, C 4 H 30 O), 1 -Pentadecanol (C 5 H 32 0), 1 -Hexadecanol ( cetyl alcohol; C 6 H 34 0), 1 heptadecanol (C 7 H 36 0), 1 -Octadecanol (stearyl alcohol; Ci 8 H 38 0), 9-cis-octadecene-1-ol (oleyl alcohol; Ci 8 H 36 0) , 9-trans-octadecene-1-ol (erucyl alcohol; CisHseO), all-cis-9,12-octadecadien-1-ol (linoleyl alcohol, Ci 8 H 3 40), all-cis-9,12,15-octadecatrien-1-ol (linolenyl alcohol, Ci 8 H 32 0) and 1-nonadecanol (Ci 9 H 40 O).
Die vorstehend genannten Fettalkohole umfassen dabei sowohl die reinen Verbindungen, als auch Isomerengemische der primären Fettalkohole. The abovementioned fatty alcohols include both the pure compounds and mixtures of isomers of the primary fatty alcohols.
Ethanolamin kann sowohl als Alkohol (AI) als auch als Aminierungsmittel (Am) eingesetzt werden. Beispiele für Diole, die als Edukte in das erfindungsgemäße Verfahren eingesetzt werden können, sind 1 ,4-Butandiol (1 ,4-Butylenglykol), 1 ,5-Pentandiol, 1 ,6-Hexandiol, 1 ,7-Heptandiol, 1 ,8-Oktandiol, 1 ,9-Nonandiol, 9-cis-Octadecen-1 ,12-diol (Ricinolalkohol; Ci8H3602), 2,4-Dimethyl-2,5-hexandiol, Hydroxypivalin- säureneopentylglykolester, Diethylenglykol, Triethylenglykol, 1 ,4-Bis-(2- hydroxyethyl)piperazin, Diisopropanolamin, N-Butyldiethanolamin, 1 ,10-Dekandiol, 1 ,12-Dodekandiol, 2,5-(Dimethanol)-furan, 1 ,4-Bis(hydroxymethyl)cyclohexan und Polyalkylenglykole, deren OH-Gruppen entweder primäre und/oder sekundäre Alkohole sein können. Als Edukte können alle bekannten Triole oder Polyole eingesetzt werden, die mindestens eine funktionelle Gruppe der Formel (-CH2-OH) oder (>CH-OH) aufweisen. Beispiele für Triole oder Polyole, die als Edukte in das erfindungsgemäße Verfahren eingesetzt werden können, sind Glycerin, Trimethylolpropan, Triisopropanolamin, Triethanolamin, Polyvinylalkohol, Polyalkylenglykole, deren OH-Gruppen entweder primäre und/oder sekundäre Alkohole sein können, 2,2-Bis(hydroxymethyl)-1 ,3- propandiol (Pentaerythrit), Sorbit, Inositol, Kohlenhydrate, Zucker, Zuckeralkohole und -polymere: wie beispielsweise Glucose, Mannose, Fructose, Ribose, Desoxyribose, Galactose, N-Acetyl-Glucosamin, Fucose, Rhamnose, Saccharose, Lactose, Cellobiose, Maltose und Amylose, Cellulose, Stärke und Xanthan. Ethanolamine can be used both as alcohol (AI) and as aminating agent (Am). Examples of diols which can be used as starting materials in the process according to the invention are 1, 4-butanediol (1, 4-butylene glycol), 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8 -Oktandiol, 1, 9-nonanediol, 9-cis-octadecene-1, 12-diol (ricinol; Ci 8 H 36 02), 2,4-dimethyl-2,5-hexanediol, Hydroxypivalin- säureneopentylglykolester, diethylene glycol, triethylene glycol, 1,4-Bis (2-hydroxyethyl) piperazine, diisopropanolamine, N-butyldiethanolamine, 1,10-decanediol, 1,12-dodecanediol, 2,5- (dimethanol) furan, 1,4-bis (hydroxymethyl) cyclohexane and polyalkylene glycols whose OH groups can be either primary and / or secondary alcohols. As starting materials, it is possible to use all known triols or polyols which have at least one functional group of the formula (-CH 2 -OH) or (> CH-OH). Examples of triols or polyols which can be used as starting materials in the process according to the invention are glycerol, trimethylolpropane, triisopropanolamine, triethanolamine, polyvinyl alcohol, polyalkylene glycols whose OH groups can be either primary and / or secondary alcohols, 2,2-bis ( hydroxymethyl) -1,3-propanediol (pentaerythritol), sorbitol, inositol, carbohydrates, sugars, sugar alcohols and polymers: such as glucose, mannose, fructose, ribose, deoxyribose, galactose, N-acetyl-glucosamine, fucose, rhamnose, sucrose , Lactose, cellobiose, maltose and amylose, cellulose, starch and xanthan gum.
Als Aminierungsmittel (Am) können praktisch alle bekannten Amine eingesetzt werden, die mindestens eine primäre oder sekundäre Aminogruppe aufweisen. As aminating agent (Am), virtually all known amines can be used which have at least one primary or secondary amino group.
Als Aminierungsmittel (Am) geeignete primäre Amine sind beispielsweise solche der allgemeinen Formel (XXI): Primary amines suitable as aminating agent (Am) are, for example, those of the general formula (XXI):
R NH2 R NH 2
(XXI), in der
,30 ausgewählt ist aus der Gruppe bestehend aus unsubstituiertem oder zumindest monosubstituiertem CrC3o-Alkyl, C5-Ci0-Cycloalkyl, C5-Ci0- Heterocyclyl, C5-Ci4-Aryl und C5-Ci4-Heteroaryl, wobei die Substituenten ausgewählt sind aus der Gruppe bestehend aus F, Cl, Br, OH, OR22, CN, NH2, NHR22, N(R22)2, COOH, COOR22, C(0)NH2, C(0)NHR22, C(0)N(R22)2, d-do-Alkyl, C5-Ci0-Cycloalkyl, C5-Ci0- Heterocyclyl, C5-Ci4-Aryl und C5-Ci4-Heteroaryl, wobei R ausgewählt ist aus CrCi0-Alkyl und C5-Ci0-Aryl. (XXI), in the , 30 is selected from the group consisting of unsubstituted or at least monosubstituted CrC 3 o-alkyl, C 5 -Ci 0 -cycloalkyl, C 5 -Ci 0 - heterocyclyl, C 5 -C 4 -aryl and C 5 -C 4 -heteroaryl wherein the substituents are selected from the group consisting of F, Cl, Br, OH, OR 22 , CN, NH 2 , NHR 22 , N (R 22 ) 2 , COOH, COOR 22 , C (0) NH 2 , C (0) NHR 22, C (0) N (R 22) 2, d-do-alkyl, C 5 -C 0 cycloalkyl, C 5 -C 0 - heterocyclyl, C 5 -C 4 aryl and C 5 - Ci 4 -heteroaryl, wherein R is selected from CrCl 0 alkyl and C 5 -C 0 aryl.
Als Aminierungsmittel (Am) sind beispielsweise die folgenden primären Amine geeignet: Methylamin, Ethylamin, n-Propylamin, iso-Propylamin, n-Butylamin, Butan-2- amin, iso-Butylamin, tert-Butylamin, n-Pentylamin, n-Hexylamin, 2-Ethylhexylamin, Anilin, Cyclohexylamin, Benzylamin, 2-Phenylethylamin, 1 -Adamantylamin, 2- Adamantylamin und Fettamine wie 1 -Heptanamin, 1 -Octanamin, 1 -Nonanamin, 1 - Decanamin, 1 -Undecanamin, 10-Undecen-1 -amin, 1 -Dodecanamin, 1 -Tridecanamin, 1 - Tetradecanamin, 1 -Pentadecanamin, 1 -Hexadecanamin, 1 Heptadecanamin, 1 - Octadecanamin, 9-cis-Octadecen-1 -amin, 9-trans-Octadecen-1 -amin, 9-cis-Octadecen- 1 ,12-diamin, all-cis-9,12-Octadecadien-1 -amin; all-cis-9,12,15-Octadecatrien-1 -amin, 1 -Nonadecanamin, 1 -Eicosanamin, 9-cis-Eicosen-1 -amin, 5,8,1 1 ,14-Eicosatetraen-1 - amin, 1 -Heneicosanamin, 1 -Docosanamin, 1 -3cis-Docosen-1 -amin und 1 -3trans- Docosen-1 -amin. Die vorstehend genannten Fettamine umfassen dabei die reinen Verbindungen, als auch Isomerengemische der primären Fettamine. Suitable aminating agents (Am) are, for example, the following primary amines: methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, butan-2-amine, isobutylamine, tert-butylamine, n-pentylamine, n-hexylamine , 2-ethylhexylamine, aniline, cyclohexylamine, benzylamine, 2-phenylethylamine, 1-adamantylamine, 2-adamantylamine and fatty amines such as 1-heptanamine, 1-octanamine, 1 -nonanamine, 1-decanamine, 1-undecanamine, 10-undecene-1 -amine, 1-dodecanamine, 1-tridecanamine, 1-tetradecanamine, 1-pentadecanamine, 1-hexadecanamine, 1-heptadecanamine, 1-octadecanamine, 9-cis-octadecene-1-amine, 9-trans-octadecene-1-amine, 9-cis-octadecene-1, 12-diamine, all-cis-9,12-octadecadien-1-amine; all-cis-9,12,15-octadecatriene-1-amine, 1-nonadecanamine, 1-eicosanamine, 9-cis-eicosene-1-amine, 5,8,1 1, 14-eicosatetraene-1-amine, 1 -Enicosanamine, 1-docosanamine, 1-cis-docosen-1-amine and 1 -3-trans-docosen-1-amine. The abovementioned fatty amines include the pure compounds as well as isomer mixtures of the primary fatty amines.
Als Aminierungsmittel (Am) besonders bevorzugte primäre Amine sind ausgewählt aus der Gruppe bestehend aus Monomethylamin, 1 -Ethylamin, 1 -Propylamin, Isopropylamin, Anilin, Ethanolamin und tert-Butylamin. As aminating agent (Am) particularly preferred primary amines are selected from the group consisting of monomethylamine, 1-ethylamine, 1-propylamine, isopropylamine, aniline, ethanolamine and tert-butylamine.
Als Aminierungsmittel (Am) geeignete sekundäre Amine sind beispielsweise solche der allgemeinen Formel (XXII): Secondary amines suitable as aminating agent (Am) are, for example, those of the general formula (XXII):
(XXII),
in der (XXII) in the
32 32
R und R unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus unsubstituiertem oder zumindest monosubstituiertem CrC3o-Alkyl, C5-Ci0-Cycloalkyl, C5-C10- Heterocyclyl, C5-Ci4-Aryl und C5-Ci4-Heteroaryl oder R31 und R32 zusammen mit dem Stickstoffatom, an das sie gebunden sind, ein fünf- bis vierzehengliedriges unsubstituiertes oder zumindest monosubstituiertes Ringsystem ausbilden, wobei die Substituenten ausgewählt sind aus der Gruppe bestehend aus F, Cl, Br, OH, OR22, CN, NH2, NHR22, N(R22)2, COOH, COOR22, C(0)NH2, C(0)NHR22, C(0)N(R22)2, C Ci0-Alkyl, C5-Ci0-Cycloalkyl, C5-Ci0-Heterocyclyl, C5-Ci4-Aryl und C5-Ci4- Heteroaryl. R and R are independently selected from the group consisting of unsubstituted or at least mono-substituted -C 3 -alkyl, C 5 -C 0 cycloalkyl, C5-C10 heterocyclyl, C 5 -C 4 aryl and C 5 -C 4 - Heteroaryl or R 31 and R 32 together with the nitrogen atom to which they are attached form a five- to vierzehengliedriges unsubstituted or at least monosubstituted ring system, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, OR 22nd , CN, NH 2 , NHR 22 , N (R 22 ) 2 , COOH, COOR 22 , C (0) NH 2 , C (O) NHR 22 , C (O) N (R 22 ) 2 , C Ci 0 - alkyl, C 5 -C 0 cycloalkyl, C 5 -C 0 heterocyclyl, C 5 -C 4 aryl and C 5 -C 4 - heteroaryl.
wobei R22 ausgewählt ist aus CrCi0-Alkyl und C5-Ci0-Aryl. wherein R 22 is selected from CrCl 0 alkyl and C 5 -C 0 aryl.
Für den Fall, dass R31 und R32 zusammen mit dem Stickstoffatom, an das sie gebunden sind, ein Ringsystem ausbilden, ist das Ringsystem bevorzugt ausgewählt aus der Gruppe bestehend aus unsubstituiertem oder zumindest monosubstituiertem Pyrrolidinyl, Pyrrolyl, Piperidinyl, wobei die Substituenten die vorstehend genannten Bedeutungen aufweisen. In the event that R 31 and R 32 together with the nitrogen atom to which they are attached form a ring system, the ring system is preferably selected from the group consisting of unsubstituted or at least monosubstituted pyrrolidinyl, pyrrolyl, piperidinyl, wherein the substituents are as above have mentioned meanings.
Als Aminierungsmittel (Am) geeignete sekundäre Amine sind beispielsweise Dimethylamin, Diethylamin, Diisopropylamin, Di-n-propylamin, Di-n-butylamin, Dihexylamin, Ditridecylamin, Di-(2-ethylhexyl)amine, Methylethylamin, Piperidin, Pyrrolidin, Morpholin, N-Methylanilin, Dibenzylamin, Tetrahydroquinolin. Examples of secondary amines suitable as aminating agent (Am) are dimethylamine, diethylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, dihexylamine, ditridecylamine, di (2-ethylhexyl) amines, methylethylamine, piperidine, pyrrolidine, morpholine, N -Methylaniline, dibenzylamine, tetrahydroquinoline.
Besonders bevorzugte sekundäre Amine sind ausgewählt aus der Gruppe bestehend aus Dimethylamin und Dibutylamin. Particularly preferred secondary amines are selected from the group consisting of dimethylamine and dibutylamine.
Komplexkatalysator complex catalyst
Im erfindungsgemäßen Verfahren wird mindestens ein Komplexkatalysator eingesetzt, der Iridium als Metallkomponente und mindestens eine Aminosäure als Liganden enthält. Bevorzugt enthält der Komplexkatalysator eine α-Aminosäure als Liganden. Das erfindungsgemäße Verfahren wird bevorzugt homogen-katalysiert durchgeführt. In the process according to the invention, at least one complex catalyst is used which contains iridium as metal component and at least one amino acid as ligand. Preferably, the complex catalyst contains an α-amino acid as a ligand. The inventive method is preferably carried out homogeneously catalyzed.
In einer bevorzugten Ausführungsform wird das erfindungsgemäße Verfahren homogen-katalysiert in Gegenwart eines Komplexkatalysators der allgemeinen Formel (I) durchgeführt:
In a preferred embodiment, the process according to the invention is carried out homogeneously catalysed in the presence of a complex catalyst of the general formula (I):
(i). in der (I). in the
R1 und R2 unabhängig voneinander Wasserstoff, unsubstituiertes oder zumindest monosubstituiertes d-Cio-Alkyl, C5-Ci0-Cycloalkyl, C5- Cio-Heterocyclyl, C5-Ci0-Aryl oder C5-Ci0-Heteroaryl sind oder R 1 and R 2 are independently hydrogen, unsubstituted or at least mono-substituted d-Cio-alkyl, C 5 -C 0 cycloalkyl, C 5 - are Cio-heterocyclyl, C 5 -C 0 aryl or C 5 -C -heteroaryl 0 or
R1 und R2 zusammen mit den Atomen, an die sie gebunden sind ein unsubstituiertes oder zumindest monosubstituiertes fünf bis zehngliedriges Ringsystem bilden, wobei die Substituenten ausgewählt sind aus der Gruppe bestehend aus NR8R9, OR10, SR11, C(0)OR12, C(0)NR13R14, NHC(NH2)2+ und unsubstituiertem oder zumindest monosubstituiertem C5-Ci0-Aryl und C5-Ci0-Heteroaryl, wobei die Substituenten ausgewählt sind aus OH und NH2; R 1 and R 2 together with the atoms to which they are attached form an unsubstituted or at least monosubstituted five to ten membered ring system, wherein the substituents are selected from the group consisting of NR 8 R 9 , OR 10 , SR 11 , C (0 ) oR 12, C (0) NR 13 R 14, NHC (NH 2) 2 + and unsubstituted or at least mono-substituted C 5 -C 0 aryl and C 5 -C 0 heteroaryl, wherein the substituents are selected from OH and NH 2 ;
X Fluorid, Chlorid, Bromid oder lodid ist; X is fluoride, chloride, bromide or iodide;
R3, R4, R5, R6 und R7 unabhängig voneinander Wasserstoff, Methyl, Ethyl, n- Propyl, iso-Propyl oder Phenyl sind; R 3 , R 4 , R 5 , R 6 and R 7 are independently hydrogen, methyl, ethyl, n-propyl, iso-propyl or phenyl;
R8, R9, R10, R11, R12, R13 und R14 unabhängig voneinander Wasserstoff oder C R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are independently hydrogen or C
Ce-Alkyl sind. Der Komplexkatalysator kann neutral, einfach oder zweifach positiv geladen sein. Bevorzugt ist der Komplexkatalysator neutral.
Der Substituent NHC(NH2)2+ stellt vorliegend einen Substituenten der nachstehenden Strukturformel dar, wobei der Substituent über die gestrichelte Bindung gebunden ist.
Besonders bevorzugt sind Komplexkatalysatoren (I), in denen R3, R4, R5, R6 und R7 Methyl sind und X Chlorid ist. Ce-alkyl. The complex catalyst may be neutral, single or double positively charged. Preferably, the complex catalyst is neutral. The substituent NHC (NH 2 ) 2 + herein represents a substituent of the structural formula below, wherein the substituent is bonded via the dashed bond. Particularly preferred are complex catalysts (I) in which R 3 , R 4 , R 5 , R 6 and R 7 are methyl and X is chloride.
Der Komplexkatalysator der allgemeinen Formel (I) weist am Iridiumzentralatom ein Stereozentrum auf. Die allgemeine Formel (I) umfasst erfindungsgemäß sämtliche Stereoisomere (in Formel (I) durch die gewellten Bindungen dargestellt) und ist nicht auf die in Formel (I) dargestellte Konfiguration beschränkt. Die Formel (I) umfasst somit auch die Stereoisomeren (laa) und (Ibb). The complex catalyst of general formula (I) has a stereogenic center on the iridium central atom. The general formula (I) includes according to the invention all stereoisomers (represented by the wavy bonds in formula (I)) and is not limited to the configuration shown in formula (I). The formula (I) thus also includes the stereoisomers (Iaa) and (Ibb).
laa Ibb laa Ibb
Gleiches gilt für die im Komplexkatalysator (I) als Liganden enthaltenen Aminosäuren. Für den Fall, dass die Aminosäuren ein oder mehrere Stereozentren enthalten, umfasst der Komplexkatalysator (I) ebenfalls sämtliche Stereoisomere. Erfindungsgemäß sind vom Komplexkatalysator (I) auch Derivate umfasst, die aus dem Komplexkatalysator durch Protonierung oder Deprotonierung erhältlich sind. The same applies to the amino acids contained in the complex catalyst (I) as ligands. In the event that the amino acids contain one or more stereocenters, the complex catalyst (I) also comprises all stereoisomers. According to the invention, the complex catalyst (I) also includes derivatives obtainable from the complex catalyst by protonation or deprotonation.
R. Krämer, K Polborn, H. Wanjek, I. Zahn, W. Beck, Chem. Ber. 1990, 123, 767 beschreiben die Herstellung und NMR-spetroskopische Untersuchung verschiedener Iridiumkomplexe, die Cp* (Pentamethylcyclopentadienyl) und α-Aminosäuren als Liganden tragen. R. Kramer, K. Polborn, H. Wanjek, I. Zahn, W. Beck, Chem. Ber. 1990, 123, 767 describe the preparation and NMR spectroscopic examination of various iridium complexes bearing Cp * (pentamethylcyclopentadienyl) and α-amino acids as ligands.
Die erfindungsgemäß eingesetzten Komplexkatalysatoren (I) lassen sich aus einer iridiumhaltigen Katalysatorvorstufe durch Umsetzung mit einer Aminosäure in Gegenwart eines Lösungsmittels und einer Base herstellen.
Als iridiumhaltige Katalysatorvorstufe sind beispielsweise [Cp*lrF2]2, [Cp*lrCI2]2, [Cp*lrBr2]2, [Cp*lrl2]2 geeignet, wobei [Cp*lrCI2]2 bevorzugt ist. Als Lösungsmittel zur Herstellung des erfindungsgemäßen Komplexkatalysators sind beispielsweise aprotische polare Lösungsmittel geeignet, wobei Acetonitril besonders bevorzugt ist. Als Base sind Alkali- oder Erdalkalicarbonate geeignet, wobei Kaliumcarbonat (K2C03) bevorzugt ist. Die Reaktion wird bevorzugt unter Schutzgasatmosphäre, wie beispielsweise Stickstoff oder Argon, durchgeführt. Die Reaktionstemperatur beträgt im Allgemeinen 0 bis 100 °C, bevorzugt 10 bis 40 °C und besonders bevorzugt 15 bis 25 °C. Die Herstellung des Komplexkatalysators (I) wird bevorzugt bei Normaldruck, das heißt dem Umgebungsdruck, durchgeführt. The complex catalysts (I) used according to the invention can be prepared from an iridium-containing catalyst precursor by reaction with an amino acid in the presence of a solvent and a base. Examples of suitable iridium-containing catalyst precursors are [Cp * IrF 2 ] 2, [Cp * IrCI 2 ] 2, [Cp * IrBr 2 ] 2, [Cp * Ir 2 ] 2, with [Cp * IrCl 2 ] 2 being preferred. Aprotic polar solvents are suitable as solvents for the preparation of the complex catalyst according to the invention, with acetonitrile being particularly preferred. As the base, alkali or alkaline earth metal carbonates are suitable, with potassium carbonate (K 2 C0 3 ) is preferred. The reaction is preferably carried out under a protective gas atmosphere, such as nitrogen or argon. The reaction temperature is generally 0 to 100 ° C, preferably 10 to 40 ° C and particularly preferably 15 to 25 ° C. The preparation of the complex catalyst (I) is preferably carried out at normal pressure, that is to say the ambient pressure.
Die als Ligand eingesetzte Aminosäure wird bevorzugt in äquimolaren Mengen bezogen auf das in der iridiumhaltigen Katalysatorvorstufe enthaltene Iridium eingesetzt. The amino acid used as the ligand is preferably used in equimolar amounts relative to the iridium contained in the iridium-containing catalyst precursor.
Die Reaktionsdauer liegt im Bereich von 5 Minuten bis 100 Stunden, bevorzugt im Bereich von 5 bis 50 Stunden, bevorzugt im Bereich von 15 bis 30 Stunden. The reaction time is in the range of 5 minutes to 100 hours, preferably in the range of 5 to 50 hours, preferably in the range of 15 to 30 hours.
Zur Isolierung des erfindungsgemäßen Komplexkatalysators (I) wird im Allgemeinen die eingesetzte Base, bevorzugt Kaliumcarbonat, abfiltriert. Anschließend wird das Lösungsmittel, bevorzugt Acetonitril, destillativ, gegebenenfalls unter vermindertem Druck, entfernt. Der so erhaltene Komplexkatalysator (I) kann, gegebenenfalls nach weiterer Aufarbeitung, als Komplexkatalysator in die Alkoholaminierung eingesetzt werden. To isolate the complex catalyst (I) according to the invention, the base used, preferably potassium carbonate, is generally filtered off. Subsequently, the solvent, preferably acetonitrile, is removed by distillation, if appropriate under reduced pressure. The complex catalyst (I) thus obtained can, if appropriate after further work-up, be used as complex catalyst in the alcohol lamination.
Als Aminosäuren sind α-Aminosäuren bevorzugt. Die Aminosäuren können sowohl als L-a-Aminosäure als auch als D-a-Aminosäure eingesetzt werden. Darüber hinaus ist es möglich, Mischungen der vorgenannten Konfigurationsisomere einzusetzen, so genannte D-L-a-Aminosäuren. As amino acids, α-amino acids are preferred. The amino acids can be used both as L-a-amino acid and as D-a-amino acid. In addition, it is possible to use mixtures of the aforementioned configuration isomers, so-called D-L-α-amino acids.
Als Aminosäuren können sowohl natürlich vorkommende Aminosäuren als auch ausschließlich synthetisch zugängliche Aminosäuren eingesetzt werden. As amino acids, both naturally occurring amino acids and exclusively synthetically accessible amino acids can be used.
Bevorzugte Aminosäuren sind ausgewählt aus der Gruppe bestehend aus Alanin, Valin, Leucin, iso-Leucin, Prolin, Tryptophan, Phenylalanin, Methonin, Glycin, Serin, Tyrosin, Threonin, Cystein, Asparagin, Glutamin, Aspartat, Glutamat, Lysin, Arginin, Histidin, Citrullin, Homocystein, Homoserin, (4R)-4-Hydroxy-Prolin, (5R)-5-Hydroxy- Lysin, Ornithin und Sarkosin. Die vorstehend genannten Aminosäuren können sowohl als L-a-Aminosäuren als auch als D-a-Aminosäuren eingesetzt werden. Darüber hinaus können auch Mischungen aus L-o und D-a-Aminosäuren der vorstehend genannten Aminosäuren eingesetzt werden
Besonders bevorzugte Aminosäuren sind ausgewählt aus der Gruppe bestehend aus Glycin, Valin, Prolin und Sarkosin. Insbesondere bevorzugte Aminosäuren sind ausgewählt aus der Gruppe bestehend aus Prolin und Sarkosin. Preferred amino acids are selected from the group consisting of alanine, valine, leucine, iso-leucine, proline, tryptophan, phenylalanine, methonine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartate, glutamate, lysine, arginine, histidine , Citrulline, homocysteine, homoserine, (4R) -4-hydroxy-proline, (5R) -5-hydroxy-lysine, ornithine and sarcosine. The abovementioned amino acids can be used both as La amino acids and as Da amino acids. In addition, mixtures of Lo and Da amino acids of the abovementioned amino acids can also be used Particularly preferred amino acids are selected from the group consisting of glycine, valine, proline and sarcosine. Particularly preferred amino acids are selected from the group consisting of proline and sarcosine.
Die vorstehenden Ausführungen und Bevorzugungen zu den Aminosäuren gelten für den Komplexkatalysator (I), der die Aminosäure enthält, entsprechend. Für die Liganden des Komplexkatalysators (I) gelten somit die vorstehenden Ausführungen und Bevorzugungen zu den Aminosäuren ebenfalls entsprechend. The above statements and preferences for the amino acids apply correspondingly to the complex catalyst (I) containing the amino acid. For the ligands of the complex catalyst (I), the above statements and preferences for the amino acids also apply accordingly.
Bevorzugt sind somit Komplexkatalysatoren (I), die Iridium als Metallkomponente, Cp* (1 ,2,3,4, 5-Pentamethylcyclopentadienylanion), Chlorid und eine Aminosäure ausgewählt aus der Gruppe bestehend aus Alanin, Valin, Leucin, iso-Leucin, Prolin, Tryptophan, Phenylalanin, Methonin, Glycin, Serin, Tyrosin, Threonin, Cystein, Asparagin, Glutamin, Aspartat, Glutamat, Lysin, Arginin, Histidin, Citrullin, Homocystein, Homoserin, (4R)-4-Hydroxy-Prolin, (5R)-5-Hydroxy-Lysin, Ornithin und Sarkosin enthalten. Preference is thus given to complex catalysts (I), the iridium as metal component, Cp * (1, 2,3,4,5-pentamethylcyclopentadienyl anion), chloride and an amino acid selected from the group consisting of alanine, valine, leucine, iso-leucine, proline , Tryptophan, phenylalanine, methonine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartate, glutamate, lysine, arginine, histidine, citrulline, homocysteine, homoserine, (4R) -4-hydroxy-proline, (5R) 5-hydroxy-lysine, ornithine and sarcosine.
Besonders bevorzugt sind Komplexkatalysatoren (I), die Iridium als Metallkomponente, Cp* (1 ,2,3,4, 5-Pentamethylcyclopentadienylanion), Chlorid und eine Aminosäure ausgewählt aus der Gruppe bestehend aus Glycin, Valin, Prolin und Sarkosin enthalten. Particularly preferred are complex catalysts (I) containing iridium as a metal component, Cp * (1, 2,3,4,5-pentamethylcyclopentadienyl anion), chloride and an amino acid selected from the group consisting of glycine, valine, proline and sarcosine.
Im Rahmen der vorliegenden Erfindung werden unter CrC30 bzw. Ci-Ci0-Alkyl bzw. d- C6-Alkyl verzweigte, unverzweigte, gesättigte und ungesättigte Gruppen verstanden. Bevorzugt sind Alkylgruppen mit 1 bis 6 Kohlenstoffatomen (CrC6-Alkyl). Mehr bevorzugt sind Alkylgruppen mit 1 bis 4 Kohlenstoffatomen (CrC4-Alkyl). In the context of the present invention, branched, unbranched, saturated and unsaturated groups are understood as meaning CrC 30 or C 1 -C 10 -alkyl or C 1 -C 6 -alkyl. Preference is given to alkyl groups having 1 to 6 carbon atoms (C 1 -C 6 -alkyl). More preferred are alkyl groups having 1 to 4 carbon atoms (C 1 -C 4 alkyl).
Beispiele für gesättigte Alkylgruppen sind Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, sec.-Butyl, tert.-Butyl, Amyl und Hexyl. Examples of saturated alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl and hexyl.
Beispiele für ungesättigte Alkylgruppen (Alkenyl, Alkinyl) sind Vinyl, Allyl, Butenyl, Ethinyl und Propinyl. Die CrCio-Alkylgruppe kann unsubstituiert oder, mit einem oder mehreren Substituenten ausgewählt aus der Gruppe F, Cl, Br, Hydroxy (OH), d-Cio-Alkoxy, C5- Cio-Aryloxy, C5-Cio-Alkylaryloxy, C5-Ci0-Heteroaryloxy enthaltend mindestens ein Heteroatom ausgewählt aus N, O, S, Oxo, C3-Ci0-Cycloalkyl, Phenyl, C5-Ci0-Heteroaryl enthaltend mindestens ein Heteroatom ausgewählt aus N, O, S, C5-Ci0-Heterocyclyl enthaltend mindestens ein Heteroatom ausgewählt aus N, O, S, Naphthyl, Amino, C Cio-Alkylamino, C5-Cio-Arylamino, C5-Ci0-Heteroarylamino enthaltend mindestens ein
Heteroatom ausgewählt aus N, O, S, Ci-Ci0-Dialkylamino, Cio-Ci2-Diarylamino, C10- C2oAlkylarylamino, d-Cio-Acyl, d-Cio-Acyloxy, N02, CrCio-Carboxy, Carbamoyl, Carboxamid, Cyano, Sulfonyl, Sulfonylamino, Sulfinyl, Sulfinylamino, Thiol, C1-C10- Alkylthiol, C5-Cio-Arylthiol oder Ci-Ci0-Alkylsulfonyl substituiert sein. Examples of unsaturated alkyl groups (alkenyl, alkynyl) are vinyl, allyl, butenyl, ethynyl and propynyl. The CrCio-alkyl group may be unsubstituted or substituted with one or more substituents selected from the group F, Cl, Br, hydroxy (OH), d-Cio-alkoxy, C 5 - Cio-aryloxy, C 5 -Cio-alkylaryloxy, C 5 -C 0 heteroaryloxy containing at least one heteroatom selected from N, O, S, oxo, C 0 -C 3 cycloalkyl, phenyl, C 5 -C 0 heteroaryl containing at least one heteroatom selected from N, O, S, C 5 -Ci 0 -Heterocyclyl containing at least one heteroatom selected from N, O, S, naphthyl, amino, C is Cio-alkylamino, C 5 -Cio-arylamino, C 5 -Ci 0 heteroarylamino containing at least one Heteroatom selected from N, O, S, Ci-Ci 0- dialkylamino, Cio-Ci2-diarylamino, C10-C2oAlkylarylamino, d-Cio-acyl, d-Cio-acyloxy, N0 2 , CrCio-carboxy, carbamoyl, carboxamide, cyano , sulfonyl, sulfonylamino, sulfinyl, Sulfinylamino, thiol, C1-C1 0 - 0 alkylsulfonyl be substituted alkylthiol, C 5 -Cio-aryl thiol, or Ci-Ci.
Unter C5-Ci0-Cycloalkyl werden vorliegend gesättigte, ungesättigte monozyklische und polyzyklische Gruppen verstanden. Beispiele für C5-Ci0-Cycloalkyl sind Cyclopentyl, Cyclohexyl oder Cycloheptyl. Die Cycloalkylgruppen können unsubstituiert oder substituiert sein mit einem oder mehreren Substituenten, wie sie vorstehend zu der Gruppe Ci-Cio-Alkyl definiert wurde. From C 5 -C 0 cycloalkyl saturated, unsaturated monocyclic and polycyclic groups are understood herein. Examples of C 5 -C 0 cycloalkyl are cyclopentyl, cyclohexyl or cycloheptyl. The cycloalkyl groups may be unsubstituted or substituted with one or more substituents as defined above for the group Ci-Cio-alkyl.
Im Rahmen der vorliegenden Erfindung wird unter C5-Ci4-Aryl bzw. C5-Ci0-Aryl ein aromatisches Ringsystem mit 5 bis 14 bzw. 5 bis 10 Kohlenstoffen verstanden. Das aromatische Ringsystem kann monozyklisch oder bizyklisch sein. Beispiele für Arylgruppen sind Phenyl, Naphthyl wie 1 -Naphthyl und 2-Naphthyl. Die Arylgruppe kann unsubstituiert oder substituiert sein, mit einem oder mehreren Substituenten wie vorstehend unter Ci-Ci0-Alkyl definiert. In the present invention, 4 aryl or C 5 -C 0 is aryl meant an aromatic ring system having 5 to 14 or 5 to 10 carbons under C 5 -C. The aromatic ring system may be monocyclic or bicyclic. Examples of aryl groups are phenyl, naphthyl, such as 1-naphthyl and 2-naphthyl. The aryl group may be unsubstituted or substituted with one or more substituents as defined above under Ci-Ci 0 -alkyl.
Im Rahmen der vorliegenden Erfindung wird unter C5-Ci4-Heteroaryl bzw. C5-C10- Heteroaryl ein heteroaromatisches System verstanden, das mindestens ein Heteroatom, ausgewählt aus der Gruppe N, O und S, enthält. Die Heteroarylgruppen können monozyklisch oder bizyklisch sein. Für den Fall, dass Stickstoff ein Ringatom ist, umfasst die vorliegende Erfindung auch N-Oxide der stickstoffenthaltenden Heteroaryle. Beispiele für Heteroaryle sind Thienyl, Benzothienyl, 1 -Naphthothienyl, Thianthrenyl, Furyl, Benzofuryl, Pyrrolyl, Imidazolyl, Pyrazolyl, Pyridyl, Pyrazinyl, Pyrimidinyl, Pyridazinyl, Indolyl, Isoindolyl, Indazolyl, Purinyl, Isoquinolinyl, Quinolinyl, Acridinyl, Naphthyridinyl, Quinoxalinyl, Quinazolinyl, Cinnolinyl, Piperidinyl, Carbolinyl, Thiazolyl, Oxazolyl, Isothiazolyl, Isoxazolyl. Die Heteroarylgruppen können unsubstituiert oder substituiert sein, mit einem oder mehreren Substituenten, die vorstehend unter Ci-Ci0-Alkyl definiert wurden. In the context of the present invention will be C 5 -C 4 -heteroaryl or C5-C1 0 - heteroaryl understood a heteroaromatic system containing at least one hetero atom selected from the group N, O, and S. The heteroaryl groups may be monocyclic or bicyclic. In the case where nitrogen is a ring atom, the present invention also includes N-oxides of the nitrogen-containing heteroaryls. Examples of heteroaryls are thienyl, benzothienyl, 1-naphthothienyl, thianthrenyl, furyl, benzofuryl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, isoindolyl, indazolyl, purinyl, isoquinolinyl, quinolinyl, acridinyl, naphthyridinyl, quinoxalinyl, Quinazolinyl, cinnolinyl, piperidinyl, carbolinyl, thiazolyl, oxazolyl, isothiazolyl, isoxazolyl. The heteroaryl groups may be unsubstituted or substituted with one or more substituents which have been defined above under Ci-Ci 0 -alkyl.
Im Rahmen der vorliegenden Erfindung werden unter C5-Ci0-Heterocyclyl fünf- bis zehngliedrige Ringsysteme verstanden, die mindestens ein Heteroatom aus der Gruppe N, O und S enthalten. Die Ringsysteme können mono- oder bizyklisch sein. Beispiele für geeignete heterozyklische Ringsysteme sind Piperidinyl, Pyrrolidinyl, Pyrrolinyl, Pyrazolinyl, Pyrazolidinyl, Morpholinyl, Thiomorpholinyl, Pyranyl, Thiopyranyl, Piperazinyl, Indolinyl, Dihydrofuranyl, Tetra hydrofuranyl, Dihydrothiophenyl, Tetrahydrothiophenyl, Dihydropyranyl und Tetra hydropyranyl. In the context of the present invention will be five- to ten-membered ring systems that contain at least one heteroatom from the group N, O and S in C 5 -C 0 heterocyclyl. The ring systems can be monocyclic or bicyclic. Examples of suitable heterocyclic ring systems are piperidinyl, pyrrolidinyl, pyrrolinyl, pyrazolinyl, pyrazolidinyl, morpholinyl, thiomorpholinyl, pyranyl, thiopyranyl, piperazinyl, indolinyl, dihydrofuranyl, tetrahydrofuranyl, dihydrothiophenyl, tetrahydrothiophenyl, dihydropyranyl and tetrahydropyranyl.
Alkoholaminierung
Der erfindungsgemäße Komplexkatalysator (I) wird bevorzugt direkt in seiner aktiven Form eingesetzt. Der Komplexkatalysator wird dazu, wie vorstehend beschreiben in einem der eigentlichen Alkoholaminierung vorgelagerten Verfahrensschritt hergestellt. Die Alkoholaminierung wird bevorzugt homogen-katalysiert durchgeführt. Alkoholaminierung The complex catalyst (I) according to the invention is preferably used directly in its active form. The complex catalyst is prepared, as described above, in a process step upstream of the actual alcohol lamination. The alcohol lamination is preferably carried out homogeneously catalyzed.
Unter homogen-katalysiert wird im Rahmen der vorliegenden Erfindung verstanden, dass der katalytisch-aktive Teil des Komplexkatalysators (I) zumindest teilweise im flüssigen Reaktionsmedium gelöst vorliegt. In einer bevorzugten Ausführungsform liegen mindestens 90 % des im Verfahren eingesetzten Komplexkatalysators im flüssigen Reaktionsmedium gelöst vor, mehr bevorzugt mindestens 95 %, insbesondere bevorzugt mehr als 99 %, am meisten bevorzugt liegt der Komplexkatalysator vollständig gelöst in flüssigen Reaktionsmedium vor (100 %), jeweils bezogen auf die Gesamtmenge im flüssigen Reaktionsmedium. Der Komplexkatalysator wird in Mengen im Bereich von 0,01 bis 20 Mol%, bevorzugt im Bereich von 0,1 bis 10 Mol% und besonders bevorzugt im Bereich von 0,2 bis 6 Mol% pro Mol OH-Gruppe, die im Edukt der Alkoholaminierung enthalten ist, eingesetzt. Die Reaktion erfolgt in der Flüssigphase im Allgemeinen bei einer Temperatur von 20 bis 250°C. Bevorzugt wird das erfindungsgemäße Verfahren bei Temperaturen im Bereich von 50 °C bis 150 °C, besonders bevorzugt im Bereich von 50 bis 130°C und insbesondere im Bereich von 70 bis 99°C durchgeführt. Die Flüssigphase kann von den Edukten, d.h. dem Alkohol (AI) oder dem Aminierungsmittel (Am) und/oder einem Lösungsmittel gebildet werden. In the context of the present invention, homogeneous catalysis is understood to mean that the catalytically active part of the complex catalyst (I) is at least partially dissolved in the liquid reaction medium. In a preferred embodiment, at least 90% of the complex catalyst used in the process is dissolved in the liquid reaction medium, more preferably at least 95%, most preferably more than 99%, most preferably the complex catalyst is completely dissolved in liquid reaction medium before (100%), respectively based on the total amount in the liquid reaction medium. The complex catalyst is used in amounts ranging from 0.01 to 20 mol%, preferably in the range of 0.1 to 10 mol%, and more preferably in the range of 0.2 to 6 mol% per mol of OH group in the starting material of Alcohol lamination is included. The reaction takes place in the liquid phase generally at a temperature of 20 to 250 ° C. The process according to the invention is preferably carried out at temperatures in the range from 50 ° C. to 150 ° C., more preferably in the range from 50 to 130 ° C. and in particular in the range from 70 to 99 ° C. The liquid phase may be derived from the starting materials, i. the alcohol (AI) or the aminating agent (Am) and / or a solvent are formed.
Die Reaktion kann im Allgemeinen bei einem Gesamtdruck von 1 bis 100 bar absolut, der sowohl der Eigendruck des Lösungsmittels bei der Reaktionstemperatur als auch der Druck eines Gases wie Stickstoff, Argon oder Wasserstoff sein kann, durchgeführt werden. Bevorzugt wird das erfindungsgemäße Verfahren bei einem Gesamtdruck im Bereich von1 bis 30 bar absolut, insbesondere bevorzugt bei einem Gesamtdruck im Bereich von 1 bis 5 bar absolut durchgeführt. In einer bevorzugten Ausführungsform wird das erfindungsgemäße Verfahren in Abwesenheit von Wassersstoff durchgeführt. Unter Abwesenheit von Wasserstoff wird erfindungsgemäß verstanden, dass der Reaktion kein zusätzlicher Wasserstoff zugeführt wird. Gegebenenfalls über andere Gase zugeführte Spuren von Wasserstoff sowie bei der Reaktion gebildete Spuren von Wasserstoff gelten als in Abwesenheit von Wasserstoff gemäß der vorliegenden Erfindung.
Die mittlere Reaktionszeit beträgt im Allgemeinen 15 Minuten bis 100 Stunden, bevorzugt 5 Stunden bis 30 Stunden. The reaction can generally be carried out at a total pressure of 1 to 100 bar absolute, which may be both the autogenous pressure of the solvent at the reaction temperature and the pressure of a gas such as nitrogen, argon or hydrogen. The process according to the invention is preferably carried out at a total pressure in the range from 1 to 30 bar absolute, more preferably at a total pressure in the range from 1 to 5 bar absolute. In a preferred embodiment, the process according to the invention is carried out in the absence of hydrogen. In the absence of hydrogen is understood according to the invention that the reaction no additional hydrogen is supplied. Optionally traces of hydrogen supplied via other gases and traces of hydrogen formed in the reaction are considered to be in the absence of hydrogen according to the present invention. The average reaction time is generally 15 minutes to 100 hours, preferably 5 hours to 30 hours.
Das Aminierungsmittel (Am) kann bezüglich der zu aminierenden Hydroxylgruppen im Alkohol (AI) in stöchiometrischen, unterstöchiometrischen oder überstöchiometrischen Mengen eingesetzt werden. Bevorzugt wird das Aminierungsmittel (Am) in stöchiometrischen Mengen eingesetzt. The aminating agent (Am) may be used in stoichiometric, substoichiometric or superstoichiometric amounts with respect to the hydroxyl groups to be aminated in the alcohol (AI). The aminating agent (Am) is preferably used in stoichiometric amounts.
Das erfindungsgemäße Verfahren kann sowohl in Gegenwart eines Lösungsmittels als auch ohne Lösungsmittel durchgeführt werden. Bevorzugt wird das erfindungsgemäße Verfahren in Gegenwart eines Lösungsmittels durchgeführt. Als Lösungsmittel eignen sich polare und unpolare Lösungsmittel, die in Reinform oder in Mischungen eingesetzt werden können. Beispielsweise kann im erfindungsgemäßen Verfahren nur ein unpolares oder nur ein polares Lösungsmittel eingesetzt werden. Es ist auch möglich, Mischungen von zwei oder mehr polaren Lösungsmitteln oder Mischungen von zwei oder mehr unpolaren Lösungsmitteln oder Mischungen aus einem oder mehr polaren mit einem oder mehr unpolaren Lösungsmitteln einzusetzen. The process according to the invention can be carried out both in the presence of a solvent and without solvent. The process according to the invention is preferably carried out in the presence of a solvent. Suitable solvents are polar and nonpolar solvents which can be used in pure form or in mixtures. For example, only a non-polar or only one polar solvent can be used in the process according to the invention. It is also possible to use mixtures of two or more polar solvents or mixtures of two or more non-polar solvents or mixtures of one or more polar with one or more non-polar solvents.
Als unpolare Lösungsmittel eignen sich beispielsweise gesättigte und ungesättigte Kohlenwasserstoffe wie Hexan, Heptan, Oktan, Cyclohexan, Benzol, Toluol, Xylol (o- Xylol, m-Xylol, p-Xylol) und Mesitylen, und lineare und zyklische Ether wie Diethylether, 1 ,4-Dioxan, MTBE (tert-Butylmethylether), Diglyme und 1 ,2-Dimethoxyethan. Bevorzugt werden Toluol, Xylole oder Mesitylen eingesetzt. Besonders bevorzugt ist Toluol. Examples of suitable nonpolar solvents are saturated and unsaturated hydrocarbons, such as hexane, heptane, octane, cyclohexane, benzene, toluene, xylene (o-xylene, m-xylene, p-xylene) and mesitylene, and linear and cyclic ethers, such as diethyl ether, 1 4-dioxane, MTBE (tert-butyl methyl ether), diglyme and 1,2-dimethoxyethane. Preference is given to using toluene, xylenes or mesitylene. Particularly preferred is toluene.
Als polare Lösungsmittel eignen sich beispielsweise Wasser, Dimethylformamid, Formamid, tert-Amylalkohol und Acetonitril. Bevorzugt wird Wasser eingesetzt. Wasser kann sowohl vor der Reaktion zugesetzt werden, bei der Reaktion als Reaktionswasser entstehen oder auch nach der Reaktion zusätzlich zum Reaktionswasser zugesetzt werden. Examples of suitable polar solvents are water, dimethylformamide, formamide, tert-amyl alcohol and acetonitrile. Preferably, water is used. Water can be added both prior to the reaction, formed in the reaction as water of reaction or added after the reaction in addition to the water of reaction.
Der Zusatz von Basen kann einen positiven Effekt auf die Produktbildung haben. Als geeignete Basen seien hier Alkalihydroxide, Erdalkalihydroxide, Alkalialkoholate, Erdalkalialkoholate, Alkalicarbonate, Erdalkalicarbonate, Alkalihydrogencarbonate und Erdalkalihydrogencarbonate genannt, von welchen 0,01 bis 100 molare Äquivalente in Bezug auf den verwendeten Metallkatalysator eingesetzt werden können. Der Einsatz von Basen ist beim erfindungsgemäßen Verfahren jedoch nicht zwingend erforderlich. In einer bevorzugten Ausführungsform wird das erfindungsgemäße Verfahren ohne den Zusatz der vorstehend genannten Basen durchgeführt.
Für die Umsetzung in der Flüssigphase werden das Aminierungsmittel (Am), der Alkohol, bevorzugt zusammen mit einem Lösungsmitteln, und dem Komplexkatalysator (I) in einen Reaktor eingeleitet. Die Zuleitung des Aminierungsmittels (Am), des Alkohols (AI), des Lösungsmittels und des Komplexkatalysator (I) kann dabei simultan oder getrennt voneinander erfolgen. Die Reaktion kann dabei kontinuierlich, in semibatch-Fahrweise, in batch-Fahrweise, rückvermischt in Produkt als Lösungsmittel oder im geraden Durchgang nicht rückvermischt durchgeführt werden. The addition of bases can have a positive effect on product formation. Suitable bases include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides, alkaline earth metal alkoxides, alkali metal carbonates, alkaline earth carbonates, alkali metal bicarbonates and alkaline earth hydrogen carbonates, of which 0.01 to 100 molar equivalents can be used with respect to the metal catalyst used. However, the use of bases is not absolutely necessary in the process according to the invention. In a preferred embodiment, the process according to the invention is carried out without the addition of the abovementioned bases. For the reaction in the liquid phase, the aminating agent (Am), the alcohol, preferably together with a solvent, and the complex catalyst (I) are introduced into a reactor. The supply of the aminating agent (Am), the alcohol (AI), the solvent and the complex catalyst (I) can be carried out simultaneously or separately. The reaction can be carried out continuously, in semibatch mode, in batch mode, back-mixed in product as a solvent or not backmixed in a straight pass.
Für das erfindungsgemäße Verfahren können prinzipiell alle Reaktoren eingesetzt werden, welche für flüssig-Reaktionen unter der gegebenen Temperatur und dem gegebenen Druck grundsätzlich geeignet sind. Geeignete Standardreaktoren für gas/flüssig- und für flüssig/flüssig-Reaktionssysteme sind beispielsweise in K.D. Henkel, "Reactor Types and Their Industrial Applications", in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, DOI: 10.1002/14356007. b04_087, Kapitel 3.3 "Reactors for gas-liquid reactions" angegeben. Als Beispiele seien genannt Rührkesselreaktoren, Rohrreaktoren oder Blasensäulenreaktoren. In principle, all reactors which are suitable in principle for liquid reactions under the given temperature and the given pressure can be used for the process according to the invention. Suitable standard reactors for gas / liquid and for liquid / liquid reaction systems are described, for example, in K.D. Henkel, "Reactor Types and Their Industrial Applications," in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, DOI: 10.1002 / 14356007. b04_087, chapter 3.3 "Reactors for gas-liquid reactions". Examples which may be mentioned stirred tank reactors, tubular reactors or bubble column reactors.
Bei der Aminierungsreaktion wird mindestens eine primäre oder sekundäre Hydroxylgruppe des Alkohols (AI) mit der Aminogruppe des Aminierungsmittels (Am) zu einem sekundären oder tertiären Amin umgesetzt, wobei sich jeweils ein Mol Reaktionswasser pro Mol umgesetzter Hydroxylgruppe bildet. In the amination reaction, at least one primary or secondary hydroxyl group of the alcohol (AI) is reacted with the amino group of the aminating agent (Am) to form a secondary or tertiary amine, each forming one mole of water of reaction per mole of hydroxyl group reacted.
Mit dem erfindungsgemäßen Verfahren sind sekundäre oder tertiäre Amine zugänglich. With the method according to the invention secondary or tertiary amines are accessible.
Sekundäre Amine (As) werden erhalten, wenn als Alkohol (AI) ein primärer oder sekundärer Monoalkohol und als Aminierungsmittel (Am) ein primäres Amin eingesetzt wird. Bevorzugt wird als Alkohol (AI) ein primärer Alkohol eingesetzt (R20 oder R21 in Formel (XX) ist Wasserstoff). Die Bildung sekundärer Amine ist exemplarisch durch die nachfolgende Reaktionsgleichung (1 ) dargestellt. Secondary amines (As) are obtained when a primary or secondary monoalcohol is used as the alcohol (AI) and a primary amine is used as the aminating agent (Am). The alcohol (AI) used is preferably a primary alcohol (R 20 or R 21 in formula (XX) is hydrogen). The formation of secondary amines is exemplified by the following reaction equation (1).
R20 CH OH + R30 NH2 ► R20 CH NH R30 R 20 CH OH + R 30 NH 2 ►R 20 CH NH R 30
| -H2O | | -H 2 O |
R21 R21 R 21 R 21
(XX) (XXI) (As) (XX) (XXI) (As)
Gegenstand der vorliegenden Erfindung ist somit auch ein Verfahren zu Herstellung sekundärer Amine (As), durch Alkoholaminierung von Alkoholen (AI), bei dem als
Alkohol ein primärer oder sekundärer Monoalkohol und als Aminierungsmittel (Am) ein primäres Amin eingesetzt wird. The present invention thus also provides a process for the preparation of secondary amines (As) by alcoholamination of alcohols (AI), in which Alcohol is a primary or secondary monoalcohol and as aminating agent (Am) a primary amine is used.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren, bei dem als Alkohol (AI) ein primärer oder sekundärer Monoalkohol und als Aminierungsmittel (Am) ein primäres Amin eingesetzt wird und als Amin (A) ein sekundäres Amin (As) erhalten wird. Another object of the present invention is a process in which a primary or secondary monoalcohol is used as the alcohol (AI) and a primary amine is used as the aminating agent (Am) and a secondary amine (As) is obtained as the amine (A).
Tertiäre Amine (At) werden erhalten, wenn als Alkohol (AI) ein primärer oder sekundärer Monoalkohol und als Aminierungsmittel (Am) ein sekundäres Amin eingesetzt wird. Bevorzugt wird als Alkohol (AI) ein primärer Alkohol eingesetzt. Die Bildung tertiärer Amine ist exemplarisch durch nachfolgende Reaktionsgleichung (2) dargestellt. Tertiary amines (At) are obtained when a primary or secondary monoalcohol is used as the alcohol (AI) and a secondary amine is used as the aminating agent (Am). The alcohol (AI) used is preferably a primary alcohol. The formation of tertiary amines is exemplified by the following reaction equation (2).
(XX) (XXII) (At) (XX) (XXII) (At)
Gegenstand der vorliegenden Erfindung ist somit auch ein Verfahren zu Herstellung tertiärer Amine (At), durch Alkoholaminierung von Alkoholen (AI), bei dem als Alkohol ein primärer oder sekundärer Monoalkohol und als Aminierungsmittel (Am) ein sekundäres Amin eingesetzt wird. Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren, bei dem als Alkohol (AI) ein primärer oder sekundärer Monoalkohol und als Aminierungsmittel (Am) ein sekundäres Amin eingesetzt wird, und als Amin (A) ein tertiäres Amin (At) erhalten wird. Tertiäre Amine (At) können darüber hinaus erhalten werden, wenn als Alkohol (AI) ein primärer oder sekundärer Monoalkohol im Überschuss, vorzugsweise mindestens doppeltmolar, und als Aminierungsmittel (Am) ein primäres Amin eingesetzt wird. Bevorzugt wird als Alkohol (AI) ein primärer Alkohol eingesetzt. Die Bildung tertiärer Amine (At) ist exemplarisch durch nachfolgende Reaktionsgleichung (3) dargestellt.
The present invention thus also provides a process for the preparation of tertiary amines (At), by Alkoholaminierung of alcohols (AI), in which a primary or secondary monoalcohol is used as alcohol and as aminating agent (Am) a secondary amine. Another object of the present invention is a process in which a primary or secondary monoalcohol is used as the alcohol (AI) and a secondary amine is used as the aminating agent (Am), and a tertiary amine (At) is obtained as the amine (A). Tertiary amines (At) can moreover be obtained if the alcohol (AI) used is a primary or secondary monoalcohol in excess, preferably at least twice, and as aminating agent (Am) a primary amine. The alcohol (AI) used is preferably a primary alcohol. The formation of tertiary amines (At) is exemplified by the following reaction equation (3).
(XX) (XXI) (At) (XX) (XXI) (At)
Gegenstand der vorliegenden Erfindung ist somit auch ein Verfahren zu Herstellung tertiärer Amine (At), durch Alkoholaminierung von Alkoholen (AI), bei dem als Alkohol ein primärer oder sekundärer Monoalkohol im Überschuss, vorzugsweise mindestens doppeltmolar, und als Aminierungsmittel (Am) ein primäres Amin eingesetzt wird. The present invention thus also provides a process for the preparation of tertiary amines (At), by Alkoholaminierung of alcohols (AI), in which as alcohol a primary or secondary monoalcohol in excess, preferably at least twice, and as aminating agent (Am) is a primary amine is used.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren, bei dem als Alkohol (AI) ein primärer oder sekundärer Monoalkohol im Überschuss, vorzugsweise mindestens doppeltmolar, und als Aminierungsmittel (Am) ein sekundäres Amin eingesetzt wird und als Amin (A) ein tertiäres Amin (At) erhalten wird. A further subject of the present invention is a process in which the alcohol (AI) used is a primary or secondary monoalcohol in excess, preferably at least twice, and as aminating agent (Am) a secondary amine and as amine (A) a tertiary amine ( At).
Tertiäre Amine (At) können darüber hinaus erhalten werden, wenn als Alkohol (AI) ein Diol mit primären oder sekundären Hydroxylgruppen und als Aminierungsmittel (Am) ein primäres Amin eingesetzt wird. Bevorzugt wird als Alkohol (AI) ein Diol (XXa) eingesetzt, das zwei primäre Hydroxylgruppen enthält. Die Bildung tertiärer Amine ist exemplarisch durch nachfolgende Reaktionsgleichung (4) dargestellt. In addition, tertiary amines (At) can be obtained when the alcohol (Al) used is a diol having primary or secondary hydroxyl groups and as aminating agent (Am) a primary amine. The alcohol (Al) used is preferably a diol (XXa) which contains two primary hydroxyl groups. The formation of tertiary amines is exemplified by the following reaction equation (4).
HO— (Alkylen)— OH + R30 NH2 HO- (alkylene) -OH + R 30 NH 2
(XXa) (XXI) (At) Unter„Alkylen" werden vorliegend unsubstituierte oder zumindest monosubstituierte bivalente Radikale verstanden. Bevorzugt sind unsubstituierte bivalente Radikale ausgewählt aus der Gruppe bestehend aus Ethylen, Trimethylen, Tetramethylen, Pentamethylen, Hexamethylen, Heptamethylen und Oktamethylen. Gegenstand der vorliegenden Erfindung ist somit auch ein Verfahren zu Herstellung tertiärer Amine (At), durch Alkoholaminierung von Alkoholen (AI), bei dem als Alkohol ein Diol mit zwei primären Hydroxylgruppen und als Aminierungsmittel (Am) ein primäres Amin eingesetzt wird.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren, bei dem als Alkohol (AI) ein Diol mit zwei primären Hydroxylgruppen und als Aminierungsmittel (Am) ein primäres Amin eingesetzt wird und als Amin (A) ein tertiäres Amin (At) erhalten wird. (XXa) (XXI) (At) Unsubstituted or at least monosubstituted bivalent radicals are understood as meaning "unsubstituted bivalent radicals" selected from the group consisting of ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene and octamethylene The present invention thus also provides a process for the preparation of tertiary amines (At) by alcoholamination of alcohols (Al), in which a diol having two primary hydroxyl groups is used as alcohol and a primary amine is used as aminating agent (Am). A further subject of the present invention is a process in which the alcohol (AI) is a diol having two primary hydroxyl groups and the aminating agent (Am) is a primary amine and the amine (A) is a tertiary amine (At).
Der bei der Umsetzung entstehende Reaktionsaustrag enthält im Allgemeinen das entsprechenden Aminierungsprodukt (d.h. ein sekundäres oder tertiäres Amin), gegebenenfalls das Lösungsmittel, den Komplexkatalysator (I), gegebenenfalls nicht umgesetzte Edukte sowie das entstandene Reaktionswasser. Beispiele The reaction effluent resulting from the reaction generally contains the corresponding amination product (i.e., a secondary or tertiary amine), optionally the solvent, the complex catalyst (I), optionally unreacted starting materials, and the resulting water of reaction. Examples
Herstellung des Komplexkatalysators (I) Preparation of the complex catalyst (I)
[Cp*lrCI2]2 (79,6 mg, 0,1 mmol), Aminosäure (0,2 mmol) und K2C03 (31 ,5 mg, 0,3 mmol) wurden in 15 ml trockenem Acetonitril (CH3CN) unter Argonatmosphäre suspendiert. Nachfolgend wurde die Mischung entgast, indem Argon durch eine Spritzenkanüle für 10 Minuten durch die Mischung geleitet wurde. Anschließend wurde für 24 Stunden bei Raumtemperatur gerührt. Die so erhaltene Mischung wurde unter Vakuum aufkonzentriert und der Rückstand wurde in trockenem Dichlormethan (CH2CI2; 10 ml) aufgenommen. Die Suspension wurde durch Celite filtriert und der Filterkuchen wurde mehrmals mit Dichlormethan (Gesamtmenge 50 ml) gewaschen. Die vereinten gelben Filtrate wurden auf ein Volumen von 5 ml aufkonzentriert und mit einem Überschuss an trockenem Pentan (30 ml) überschichtet. Nach 48 Stunden wurde das Lösungsmittelgemisch dekantiert und die Kristalle wurden mit trockenem Pentan gewaschen. Der so erhaltene Komplexkatalysator (I) wurde unter Vakuum getrocknet unter Erhalt eines gelben oder orangenen Feststoffs. Die Bildung des Komplexkatalysators ist durch die nachfolgende Reaktionsgleichung (5) wiedergegeben [Cp * IrcI 2 ] 2 (79.6 mg, 0.1 mmol), amino acid (0.2 mmol) and K 2 CO 3 (31, 5 mg, 0.3 mmol) were dissolved in 15 mL of dry acetonitrile (CH 2 Cl 2 ) 3 CN) was suspended under argon atmosphere. Subsequently, the mixture was degassed by passing argon through the mixture through a syringe cannula for 10 minutes. It was then stirred for 24 hours at room temperature. The resulting mixture was concentrated under vacuum and the residue was taken up in dry dichloromethane (CH 2 Cl 2 , 10 ml). The suspension was filtered through Celite and the filter cake was washed several times with dichloromethane (total amount 50 ml). The combined yellow filtrates were concentrated to a volume of 5 ml and overlaid with an excess of dry pentane (30 ml). After 48 hours, the solvent mixture was decanted and the crystals were washed with dry pentane. The complex catalyst (I) thus obtained was dried under vacuum to obtain a yellow or orange solid. The formation of the complex catalyst is represented by the following reaction equation (5)
K2CQ3 K 2 CQ 3
[Cp*lrCI2]2 + Aminosäure (AA) Cp*lr(AA)CI [Cp * IrcI 2 ] 2 + amino acid (AA) Cp * Ir (AA) Cl
[CH3CN], rt [CH 3 CN], rt
Es wurden die Komplexkatalysatoren la, Ib, Ic und Id synthetisiert,„Gly" bedeutet L- Glycin.„Val" bedeutet L-Valin.„Sar" bedeutet L-Sarkosin und„Pro" bedeutet L-Prolin. „d.r" gibt das Diastereomerenverhältnis an,„rt" bedeutet Raumtemperatur.
The complex catalysts Ia, Ib, Ic and Id were synthesized, "Gly" means L-glycine, "Val" means L-valine, "Sar" means L-sarcosine, and "Pro" means L-proline. "Dr" indicates the diastereomer ratio, "rt" means room temperature.
la Ib Ic Id la Ib Ic Id
Cp*lr(Gly)CI Cp*lr(Val)CI Cp*lr(Sar)CI Cp*lr(Pro)CI Cp * Ir (Gly) Cl Cp * Ir (Val) CI Cp * Ir (Sar) CI Cp * Ir (Pro) Cl
79% 78% 74% 71 % d.r. = 1 : 0 d.r. = 1 : 1 d.r. = 1 : 0 d.r. = 6 : 1 79% 78% 74% 71% d. = 1: 0 d. = 1: 1 d. = 1: 0 d. = 6: 1
Die analytische Charakterisierung der Komplexkatalysatoren la, Ib, Ic und Id ist nachfolgend angegeben. Cp*lr(Glv)CI (la): The analytical characterization of the complex catalysts Ia, Ib, Ic and Id is given below. Cp * Ir (Glv) Cl (la):
1H-NMR (MeOD, 500 MHz): δ = 1 ,70 (s, 15 H, 5xCH3), 3,40 (dd, 2H, CH2, J = 15,6 Hz, J = 15,3 Hz), 1 H-NMR (MeOD, 500 MHz): δ = 1.70 (s, 15 H, 5xCH 3 ), 3.40 (dd, 2H, CH 2 , J = 15.6 Hz, J = 15.3 Hz )
13C-NMR (MeOD, 125,7 MHz): δ = 9,1 (5*CH3), 45,9 (CH2), 85,6 (5xCq), 186,9 (Cq). MS (FAB): m/z = 438,6. 13 C-NMR (MeOD, 125.7 MHz): δ = 9.1 (5 * CH 3 ), 45.9 (CH 2 ), 85.6 (5xC q ), 186.9 (C q ). MS (FAB): m / z = 438.6.
Elementaranalyse: ber. C 32,98%, H 4,38%, N 3,21 %; gef. C 31 ,49%, H 4,32%, N 2,97%. Elemental analysis: calc. C 32.98%, H 4.38%, N 3.21%; gef. C 31, 49%, H 4.32%, N 2.97%.
Cp*lr(Val)CI (Ib): Cp * Ir (Val) CI (Ib):
1H-NMR (MeOD, 500 MHz): δ = 0,91 (dd, 3H, CH3, J = 6,8 Hz, J = 25,1 Hz), 1 ,07 (m, 3H, CH3), 1 ,71 (s, 15 H, 5xCH3), 2,29 (m, 1 H, CH), 3,25 (m, 1 H, CH), 1 H-NMR (MeOD, 500 MHz): δ = 0.91 (dd, 3H, CH 3 , J = 6.8 Hz, J = 25.1 Hz), 1, 07 (m, 3H, CH 3 ) , 1, 71 (s, 15 H, 5xCH 3), 2.29 (m, 1 H, CH), 3.25 (m, 1 H, CH),
13C-NMR (MeOD, 125,7 MHz): δ = 9,1 (5xCH3), 17,0 (CH3), 19,3 (CH3), 32,4 (CH), 61 ,8 (CH), 86,5 (5xCq), 184,4 (Cq). 13 C-NMR (MeOD, 125.7 MHz): δ = 9.1 (5xCH 3 ), 17.0 (CH 3 ), 19.3 (CH 3 ), 32.4 (CH), 61, 8 ( CH), 86.5 (5xC q ), 184.4 (C q ).
MS (FAB): m/z = 480,2. MS (FAB): m / z = 480.2.
Elementaranalyse: ber. C 37,61 %, H 5,26%, N 2,92%; gef. 37,05%, H 5,40%, N 2,88%. Elemental analysis: calc. C 37.61%, H 5.26%, N 2.92%; gef. 37.05%, H 5.40%, N 2.88%.
Cp*lr(Sar)CI (Ic): Cp * Ir (Sar) CI (Ic):
1H-NMR (MeOD, 500 MHz): δ = 1 ,67 (s, 15 H, 5xCH3), 2,78 (s, 3H, CH3), 3,39 (dd, 2H, CH2, J = 14,8 Hz, J = 61 ,8 Hz), 1 H-NMR (MeOD, 500 MHz): δ = 1.67 (s, 15 H, 5xCH 3 ), 2.78 (s, 3H, CH 3 ), 3.39 (dd, 2H, CH 2 , J = 14.8 Hz, J = 61, 8 Hz),
13C-NMR (MeOD, 125,7 MHz): δ = 9,3 (5xCH3), 40,8 (CH2), 57,0 (CH3), 86,2 (5xCq), 185,7 (Cq). 1 3 C-NMR (MeOD, 125.7 MHz): δ = 9.3 (5xCH 3 ), 40.8 (CH 2 ), 57.0 (CH 3 ), 86.2 (5xC q ), 185, 7 (C q ).
MS (FAB): m/z = 452,1 . MS (FAB): m / z = 452.1.
Elementaranalyse: ber. C 34,62%, H 4,69%, N 3,1 1 %; gef. C 33,50%, H 4,50%, N 2,92%. Elemental analysis: calc. C 34.62%, H 4.69%, N 3.1 1%; gef. C 33.50%, H 4.50%, N 2.92%.
Cp*lr(Pro)CI (Id):
1H-NMR (MeOD, 500 MHz): δ = 1 ,70 (s, 15 H, 5*CH3), 1 ,78 - 1 ,97 (m, 4H, 2*CH2), 2,19 (m, 2H, CH2), 2,89 (m, 1 H, CH2), 3,64 (m, 1 H, CH2), 3,92 (m, 1 H, CH), Cp * lr (Pro) CI (Id): 1 H-NMR (MeOD, 500 MHz): δ = 1.70 (s, 15 H, 5 * CH 3 ), 1.78-1.197 (m, 4H, 2 * CH 2 ), 2.19 ( m, 2H, CH 2 ), 2.89 (m, 1H, CH 2 ), 3.64 (m, 1H, CH 2 ), 3.92 (m, 1H, CH),
13C-NMR (MeOD, 125,7 MHz): δ = 9,4 (5*CH3), 27,9 (CH2), 30,2 (CH2), 56,3 (CH2), 64,0 (CH), 85,8 (5xCq), 188,4 (Cq). 1 3 C-NMR (MeOD, 125.7 MHz): δ = 9.4 (5 * CH 3 ), 27.9 (CH 2 ), 30.2 (CH 2 ), 56.3 (CH 2 ), 64.0 (CH), 85.8 (5xC q ), 188.4 (C q ).
MS (FAB): m/z = 478,2. MS (FAB): m / z = 478.2.
Elementaranalyse: ber. C 37,77%, H 4,86%, N 2,94%; gef. C 38,52%, H 5,15%, N 2,83%. Elemental analysis: calc. C 37.77%, H 4.86%, N 2.94%; gef. C 38.52%, H 5.15%, N 2.83%.
Alkoholaminierung von 1 -Octylamin (1 ) mit 1 -Hexanol (2) In einem ACE-Druckrohr wurden 1 -Hexanol (1 ,0 mmol, 102,2 mg), 1 -Octylamin (1 ,0 mmol, 128,2 mg) und der jeweilige Komplexkatalysator (2 mol-%) in 0,5 ml trockenem Toluol (wurde die Reaktion in Wasser durchgeführt, wurden 0,1 mL Wasser anstatt des Toluols verwendet - siehe Tabelle 7) unter Argonatmosphäre aufgelöst. Das Reaktionsgefäß wurde mit einem Teflonstopfen verschlossen und unter Rühren auf die angegebene Temperatur für 24 Stunden erhitzt. Nachfolgend wurde die Mischung auf Raumtemperatur abgekühlt und mit Wasser (10 ml) verdünnt. Das Rohprodukt wurde mit Dichlormethan (2 x 10 ml) extrahiert. Die vereinigten organischen Phasen wurden mit einer gesättigten Natriumhydrogencarbonatlösung und einer gesättigten Kochsalzlösung gewaschen und über Natriumsulfat (Na2S04) getrocknet. Nach Filtration wurde das Lösungsmittel unter Vakuum destilliert und das erhaltene Produkt der Alkoholaminierung wurde durch Säulenchromatographie über Florisil (Magnesiumsilikat) mit einer Mischung aus Dichlormethan und Methanol im Verhältnis 30:1 bis 10:1 gereinigt. Nach Entfernung des Lösungsmittels wurde eine farblose Flüssigkeit erhalten.. Die Umsetzung folgt der Reaktionsgleichung (6) (nicht stöchiometrische Darstellung)
Alcohol lamination of 1-octylamine (1) with 1-hexanol (2) In an ACE pressure tube 1-hexanol (1, 0 mmol, 102.2 mg), 1-octylamine (1, 0 mmol, 128.2 mg) and the respective complex catalyst (2 mol%) in 0.5 ml of dry toluene (when the reaction was carried out in water, 0.1 ml of water was used instead of the toluene - see Table 7) under an argon atmosphere. The reaction vessel was sealed with a Teflon stopper and heated with stirring to the indicated temperature for 24 hours. Subsequently, the mixture was cooled to room temperature and diluted with water (10 ml). The crude product was extracted with dichloromethane (2 x 10 ml). The combined organic phases were washed with a saturated sodium bicarbonate solution and a saturated saline solution and dried over sodium sulfate (Na 2 S0 4 ). After filtration, the solvent was distilled under vacuum and the resulting product of the alcohol lamination was purified by column chromatography on Florisil (magnesium silicate) with a 30: 1 to 10: 1 mixture of dichloromethane and methanol. After removal of the solvent, a colorless liquid was obtained. The reaction follows the reaction equation (6) (non-stoichiometric representation).
Cp*lrCI(AA) (2 mol%) Cp * IrCl (AA) (2 mol%)
^NH2 + J& 3 4 ^ NH 2 + J & 3 4
:iOH : IOH
Die Ergebnisse sind in der nachfolgenden Tabelle 1 wiedergegeben.
Tabelle 1 The results are shown in Table 1 below. Table 1
Selektivität selectivity
BeiTemp. Umsatz BeiTemp. sales
Komplexkatalysator 3 4 5 6 Complex catalyst 3 4 5 6
spiel [°C] (%) play [° C] (%)
(%) (%) (%) (%) (%) (%) (%) (%)
1 Cp*lr(Gly)CI (la) 125 100 53 12 21 141 Cp * Ir (Gly) Cl (Ia) 125 100 53 12 21 14
2 Cp*lr(Val)CI (Ib) 125 100 59 12 14 152 Cp * Ir (Val) CI (Ib) 125 100 59 12 14 15
3 Cp*lr(Sar)CI (Ic) 125 100 44 20 14 223 Cp * Ir (Sar) CI (Ic) 125 100 44 20 14 22
4 Cp*lr(Pro)CI (Id) 125 100 40 15 16 294 Cp * Ir (Pro) CI (Id) 125 100 40 15 16 29
5 Cp*lr(Gly)CI (la) 105 100 82 12 2 4 5 Cp * Ir (Gly) Cl (Ia) 105 100 82 12 2 4
6 Cp*lr(Val)CI (Ib) 105 100 95 5 0 0 6 Cp * Ir (Val) CI (Ib) 105 100 95 5 0 0
7 Cp*lr(Sar)CI (Ic) 105 100 89 1 1 0 0 7 Cp * Ir (Sar) CI (Ic) 105 100 89 1 1 0 0
8 Cp*lr(Pro)CI (Id) 105 100 50 13 17 208 Cp * Ir (Pro) CI (Id) 105 100 50 13 17 20
9 Cp*lr(Gly)CI (la) 95 100 94 3 3 0 9 Cp * Ir (Gly) Cl (Ia) 95 100 94 3 3 0
10 Cp*lr(Val)CI (Ib) 95 93 94 6 0 0 10 Cp * Ir (Val) CI (Ib) 95 93 94 6 0 0
1 1 Cp*lr(Sar)CI (Ic) 95 100 97 3 <1 0 1 1 Cp * Ir (Sar) CI (Ic) 95 100 97 3 <1 0
12 Cp*lr(Pro)CI (Id) 95 100 86 8 6 0 12 Cp * Ir (Pro) CI (Id) 95 100 86 8 6 0
13 Glycin 95 0 0 0 0 0 13 glycine 95 0 0 0 0 0
14 [Cp*lrCI2]2 95 29 19 0 0 0 14 [Cp * IrcI 2 ] 2 95 29 19 0 0 0
Alle getesteten Komplexkatalysatoren la, Ib, Ic und Id zeigen bei Temperaturen von 125 °C und 105 °C eine gute katalytische Aktivität. Bei diesen Temperaturen wurde in allen Fällen ein Vollumsatz der eingesetzten Edukte erreicht. Allerdings wurde neben der Bildung des gewünschten Zielprodukts /V-Hexyloctylamin (3) auch die Bildung des sekundären Amins (4) und der tertiären Amine (5 und 6) beobachtet. Eine Absenkung der Temperatur auf 95 °C verbesserte die Selektivität der Bildung des gewünschten Zielprodukts (3) signifikant (siehe Beispiele 9 bis 12 in Tabelle 1 ). All the complex catalysts la, Ib, Ic and Id tested show good catalytic activity at temperatures of 125 ° C. and 105 ° C. At these temperatures, full conversion of the educts used was achieved in all cases. However, besides the formation of the desired target product / V-hexyloctylamine (3), the formation of the secondary amine (4) and the tertiary amines (5 and 6) was also observed. Lowering the temperature to 95 ° C significantly improved the selectivity of formation of the desired target product (3) (see Examples 9 to 12 in Table 1).
Beim Einsatz von einer Aminosäure (Glycin; siehe Beispiel 13 in Tabelle 1 ) wurde kein Umsatz beobachtet. In Beispiel 15 in Tabelle 1 wurde die Reaktion in Gegenwart von [Cp*lrCI2]2 bei 95 °C durchgeführt. Hierbei wurden nur sehr geringe Umsätze der Edukte und eine unzufriedenstellende Selektivität in Bezug auf das Zielprodukt N- Hexyloctylamin (3) erreicht. When using one amino acid (glycine, see Example 13 in Table 1), no conversion was observed. In Example 15 in Table 1, the reaction was carried out in the presence of [Cp * IrCI 2 ] 2 at 95 ° C. In this case, only very low conversion of the starting materials and unsatisfactory selectivity with respect to the target product N-hexyloctylamine (3) were achieved.
Das erhaltene Zielprodukt /V-Hexyloctylamin (3) wurde analytisch charakterisiert. Die Ergebnisse sind nachfolgend angegeben. The obtained target product / V-hexyloctylamine (3) was characterized analytically. The results are given below.
1H-NMR (CDCIs, 200 MHz): δ = 0,86 (t, 6H, 2*CH3, J = 6,1 Hz), 1 ,26 (m, 16H, 8*CH2), 1 ,60 (m, 4H, 2*CH2), 2,66 (t, 4H, 2*CH2, J = 7,4 Hz), 4,07 (bs, 1 H, NH),
13C-NMR (CDCI3, 50,3 MHz): δ = 14,0 (CH3), 14,0 (CH3), 22,5 (CH2), 22,6 (CH2), 26,9 (CH2), 27,3 (CH2), 28,9 (CH2), 29,0 (CH2), 29,2 (CH2), 29,4 (CH2), 31 ,6 (CH2), 31 ,8 (CH2), 49,5 (2xCH2). 1 H-NMR (CDCIs, 200 MHz): δ = 0.86 (t, 6H, 2 * CH 3 , J = 6.1 Hz), 1, 26 (m, 16H, 8 * CH 2 ), 1, 60 (m, 4H, 2 * CH 2 ), 2.66 (t, 4H, 2 * CH 2 , J = 7.4 Hz), 4.07 (bs, 1 H, NH), 13 C-NMR (CDCl 3 , 50.3 MHz): δ = 14.0 (CH 3 ), 14.0 (CH 3 ), 22.5 (CH 2 ), 22.6 (CH 2 ), 26, 9 (CH 2 ), 27.3 (CH 2 ), 28.9 (CH 2 ), 29.0 (CH 2 ), 29.2 (CH 2 ), 29.4 (CH 2 ), 31, 6 ( CH 2 ), 31, 8 (CH 2 ), 49.5 (2xCH 2 ).
MS (El): m/z (%): 213 (9), 142 (98), 1 14 (100), 100 (3), 84 (4), 70 (7), 57 (12). MS (El): m / z (%): 213 (9), 142 (98), 14 (100), 100 (3), 84 (4), 70 (7), 57 (12).
HR-MS: berechnet: 213,2457 gefunden: 213,2438. HR-MS: calculated: 213.2457 found: 213.2438.
Zur Untersuchung der Reaktivität der Komplexkatalysatoren la, Ic und Id wurde die Alkoholaminierung bei 95 °C durchgeführt und nach 6-stündiger Reaktionsdauer abgebrochen. Bei dieser Reaktionsführung wurde ein Reaktionsgemisch erhalten, das durch die nachfolgende Reaktionsgleichung (7) wiedergegeben ist. To investigate the reactivity of the complex catalysts Ia, Ic and Id, the alcohol lamination was carried out at 95 ° C and terminated after 6 hours of reaction. In this reaction procedure, a reaction mixture represented by the following reaction equation (7) was obtained.
Die Ergebnisse sind in der nachfolgenden Tabelle 2 wiedergegeben. The results are shown in Table 2 below.
Tabelle 2 Table 2
Selektivität selectivity
Temp. Umsatz Temp. Turnover
Beispiel Komplexkatalysator 3a 3 4 5 Example complex catalyst 3a 3 4 5
[°C] (%) [° C] (%)
(%) (%) (%) (%) (%) (%) (%) (%)
15 Cp*lr(Gly)CI (la) 95 34 19 79 2 <115 Cp * Ir (Gly) Cl (Ia) 95 34 19 79 2 <1
16 Cp*lr(Sar)CI (Ic) 95 65 9 90 0 116 Cp * Ir (Sar) CI (Ic) 95 65 9 90 0 1
17 Cp*lr(Pro)CI (Id) 95 90 8 82 7 3 17 Cp * lr (Pro) CI (Id) 95 90 8 82 7 3
Nach 6 Stunden konnte das Zwischenprodukt (3a) detektiert werden. Bei 6-stündiger Reaktionszeit wurden Umsätze zwischen 34 und 90% erreicht. Die Selektivität im Bezug auf das Zielprodukt (3) lag im Bereich von 79 bis 90%. After 6 hours, the intermediate (3a) could be detected. With a 6-hour reaction time, sales between 34 and 90% were achieved. The selectivity for the target product (3) ranged from 79 to 90%.
Herstellung sekundärer Amine (As) aus Anilinderivaten als Aminierungsmittel (Am) Preparation of secondary amines (As) from aniline derivatives as aminating agent (Am)
Die in Tabelle 3 aufgeführten Anilinderivate wurden mit 1 -Hexanol umgesetzt. Die Umsetzung erfolgte dabei gemäß der vorstehend beschriebenen Vorschrift. Als Lösungsmittel wurde Toluol eingesetzt, als Katalysator wurde Cp*lr(Pro)CI (2 mol-%) eingesetzt. Die Reaktion wurde in Toluol bei 95 °C für 24 Stunden durchgeführt. Die Umsetzung folgt dabei der allgemeinen Reaktionsgleichung (8).
The aniline derivatives listed in Table 3 were reacted with 1-hexanol. The reaction was carried out according to the procedure described above. Toluene was used as solvent, Cp * lr (Pro) Cl (2 mol%) was used as the catalyst. The reaction was carried out in toluene at 95 ° C for 24 hours. The reaction follows the general reaction equation (8).
18-22 18-22
Tabelle 3 Table 3
Beispiel R Ausbeute (%) Example R Yield (%)
18 H 98 18 H 98
19 p-OMe 99 19 p-OMe 99
20 p-CI 85 20 p-CI 85
21 o,p-Me 83 21 o, p-Me 83
22 p-C02Me 86 22 p-C0 2 Me 86
Die gewünschten Zielprodukte (18 bis 22) wurden in guten Ausbeuten erhalten. Die Bildung von /V-dialkylierten Anilinderivaten wurde nicht beobachtet. The desired target products (18 to 22) were obtained in good yields. The formation of / V-dialkylated aniline derivatives was not observed.
Analog zu der zuvor beschriebenen Reaktion wurden Anilinderivate mit Benzylalkohol umgesetzt. Die Umsetzung erfolgte dabei gemäß der nachfolgenden Reaktionsgleichung (9) Analogously to the reaction described above, aniline derivatives were reacted with benzyl alcohol. The reaction was carried out according to the following reaction equation (9)
23-27 Die Ergebnisse sind in Tabelle (4) wiedergegeben. Auch hier wurden gute Ausbeuten der Zielprodukte (23 bis 27) erhalten. 23-27 The results are shown in Table (4). Again, good yields of the target products (23 to 27) were obtained.
Tabelle 4 Table 4
Beispiel R Ausbeute (%) Example R Yield (%)
23 H 97 23 H 97
24 p-OMe 100 24 p-OMe 100
25 p-CI 95 25 p-CI 95
26 o,p-Me 81 26 o, p-Me 81
27 p-C02Me 82
Darüber hinaus wurde Anilin mit verschiedenen Benzylalkoholderivaten umgesetzt. Die Umsetzung folgt dabei der nachfolgenden Reaktionsgleichung (10) 27 p-C0 2 Me 82 In addition, aniline was reacted with various benzyl alcohol derivatives. The reaction follows the following reaction equation (10)
28-30 28-30
Die Ergebnisse sind in Tabelle 5 wiedergegeben. Tabelle 5 The results are shown in Table 5. Table 5
Beispiel R Ausbeute (%) Example R Yield (%)
28 OMe 93 28 OMe 93
29 Cl 90 29 Cl 90
30 C02Me 96 30 C0 2 Me 96
Die Umsetzung wurde hier bei 100 °C durchgeführt. Die sekundären Amine (As) wurden in Ausbeuten von > 90% erhalten. The reaction was carried out here at 100 ° C. The secondary amines (As) were obtained in yields of> 90%.
Die Umsetzung weiterer Alkohole (AI) mit weiteren Aminierungsmitteln (Am) ist in der nachfolgenden Tabelle (6) wiedergegeben. Die Umsetzung erfolgte in Toluol als Lösungsmittel in Gegenwart von 2 mol-% Cp*lr(Pro)CI als Katalysator. Die Reaktionsbedingungen und Ausbeuten sind in der nachfolgenden Tabelle (6) angegeben.
The reaction of further alcohols (AI) with further aminating agents (Am) is reproduced in Table (6) below. The reaction was carried out in toluene as solvent in the presence of 2 mol% Cp * Ir (Pro) Cl as catalyst. The reaction conditions and yields are given in the following table (6).
Tabelle 6 Table 6
Die Ergebnisse der Alkoholaminierung in Wasser als Lösungsmittel sind in Tabelle 7 angegeben. The results of the alcohol lamination in water as solvent are given in Table 7.
Tabelle 7 Table 7
Selektivitäten und Ausbeuten wurden entweder durch Isolation des Produktes bestimmt oder mittels GC unter Verwendung des internen Standards Biphenyl. Selectivities and yields were determined either by isolation of the product or by GC using the internal standard biphenyl.
Die Analysen der Reaktionsmischungen per GC-MS wurden an einem Agilent 19091 S- 433 modularen GC mit einem Kapillarinjektionssystem im Split-Modus und einem Flammenionisationsdetektor durchgeführt. Es wurde eine Standard HP-5 Kapillarsäule (Agilent 19091 S-433, 5% Phenylmethylsiloxan, Kapillare 30 m χ 250 μηι χ 0.25 m) verwendet (Fluss Helium 1 .0 mL/min, Temperaturprogramm: initial 50 °C für 2 min, 10 °C/min bis 280 °C, 280 °C für 2 min).
Analyzes of the reaction mixtures by GC-MS were performed on an Agilent 19091 S-433 modular GC with a split-mode capillary injection system and a flame ionization detector. A standard HP-5 capillary column (Agilent 19091 S-433, 5% phenylmethylsiloxane, capillary 30 m χ 250 μηι χ 0.25 m) was used (flow helium 1 .0 mL / min, temperature program: initial 50 ° C for 2 min, 10 ° C / min to 280 ° C, 280 ° C for 2 min).
Claims
Patentansprüche claims
1 . Verfahren zur Herstellung von Aminen (A) durch Alkoholaminierung von Alkoholen (AI) mit einem Aminierungsmittel (Am) unter Wasserabspaltung, wobei die Alkoholaminierung in Gegenwart eines Komplexkatalysators durchgeführt wird, der Iridium und eine Aminosäure enthält. 1 . A process for the preparation of amines (A) by alcoholic amination of alcohols (AI) with an amination agent (Am) with elimination of water, wherein the alcohol lamination is carried out in the presence of a complex catalyst containing iridium and an amino acid.
2. Verfahren gemäß Anspruch 1 , wobei der Komplexkatalysator eine a- Aminosäure enthält. 2. The method according to claim 1, wherein the complex catalyst contains an α-amino acid.
3. Verfahren gemäß Anspruch 1 oder 2, wobei das Verfahren homogen-katalysiert durchgeführt wird. 4. Verfahren gemäß einem der Ansprüche 1 bis 3, wobei das Verfahren in Gegenwart eines Komplexkatalysators der allgemeinen Formel (I) durchgeführt wird 3. The method according to claim 1 or 2, wherein the method is carried out homogeneous-catalyzed. 4. The method according to any one of claims 1 to 3, wherein the process is carried out in the presence of a complex catalyst of the general formula (I)
(I), in der (I), in the
R1 und R2 unabhängig voneinander Wasserstoff, unsubstituiertes oder zumindest monosubstituiertes d-Cio-Alkyl, C5-Ci0-Cycloalkyl, C5-R 1 and R 2 are independently hydrogen, unsubstituted or at least mono-substituted d-Cio-alkyl, C 5 -C 0 cycloalkyl, C 5 -
Cio-Heterocyclyl, C5-Ci0-Aryl oder C5-Ci0-Heteroaryl sind oder Cio-heterocyclyl, C 5 -C 0 aryl or C 5 -C 0 or heteroaryl are
R1 und R2 zusammen mit den Atomen, an die sie gebunden sind ein unsubstituiertes oder zumindest monosubstituiertes fünf bis zehngliedriges Ringsystem bilden, wobei die Substituenten ausgewählt sind aus der Gruppe bestehend aus NR8R9, OR10, SR11, C(0)OR12, C(0)NR13R14,
NHC(NH2)2+ und unsubstituiertem oder zumindest monosubstituiertem C5-Ci0-Aryl und C5-Cio-Heteroaryl, wobei die Substituenten ausgewählt sind aus OH und NH2; R 1 and R 2 together with the atoms to which they are attached form an unsubstituted or at least monosubstituted five to ten membered ring system, wherein the substituents are selected from the group consisting of NR 8 R 9 , OR 10 , SR 11 , C (0 ) OR 12 , C (0) NR 13 R 14 , NHC (NH 2) 2 + and unsubstituted or at least mono-substituted C 5 -C 0 aryl and C 5 -Cio-heteroaryl, wherein the substituents are selected from OH and NH 2;
X Fluorid, Chlorid, Bromid oder lodid ist; X is fluoride, chloride, bromide or iodide;
R3, R4, R5, R6 und R7 unabhängig voneinander Wasserstoff, Methyl, Ethyl-, n- Propyl, iso-Propyl oder Phenyl sind; R 3 , R 4 , R 5 , R 6 and R 7 are independently hydrogen, methyl, ethyl, n-propyl, iso-propyl or phenyl;
R8, R9, R10, R11, R12, R13 und R14 unabhängig voneinander Wasserstoff oder C R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are independently hydrogen or C
Ce-Alkyl sind. Ce-alkyl.
Verfahren gemäß Anspruch 4, wobei in der allgemeinen Formel (I) R3, R4, R5, R6 und R7 Methyl sind und X Chlorid ist. The process according to claim 4, wherein in the general formula (I), R 3 , R 4 , R 5 , R 6 and R 7 are methyl and X is chloride.
Verfahren gemäß einem der Ansprüche 1 bis 5, wobei die Aminosäure ausgewählt ist aus der Gruppe bestehend aus Alanin, Valin, Leucin, iso-Leucin, Prolin, Tryptophan, Phenylalanin, Methonin, Glycin, Serin, Tyrosin, Threonin, Cystein, Asparagin, Glutamin, Aspartat, Glutamat, Lysin, Arginin, Histidin, Citrullin, Homocystein, Homoserin, (4R)-4-Hydroxy-Prolin, (5R)-5-Hydroxy- Lysin, Ornithin und Sarkosin. A method according to any one of claims 1 to 5, wherein the amino acid is selected from the group consisting of alanine, valine, leucine, iso-leucine, proline, tryptophan, phenylalanine, methonine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine , Aspartate, glutamate, lysine, arginine, histidine, citrulline, homocysteine, homoserine, (4R) -4-hydroxy-proline, (5R) -5-hydroxy-lysine, ornithine and sarcosine.
Verfahren gemäß einem der Ansprüche 1 bis 6, wobei das Verfahren bei Temperaturen im Bereich von 50 °C bis 150 °C, besonders bevorzugt im Bereich von 50 bis 130 °C und insbesondere im Bereich von 70 bis 99 °C durchgeführt wird. Method according to one of claims 1 to 6, wherein the method at temperatures ranging from 50 ° C to 150 ° C, more preferably in the range of 50 to 130 ° C and in particular in the range of 70 to 99 ° C is performed.
Verfahren gemäß einem der Ansprüche 1 bis 7, wobei das Verfahren ohne den Zusatz einer Base ausgewählt aus der Gruppe bestehend aus Alkalihydroxiden, Erdalkalihydroxiden, Alkalialkoholaten, Erdalkalialkoholaten, Alkalicarbonaten, Erdalkalicarbonaten, Alkalihydrogencarbonaten undA process according to any one of claims 1 to 7, wherein the process does not involve the addition of a base selected from the group consisting of alkali hydroxides, alkaline earth hydroxides, alkali alcoholates, alkaline earth alcoholates, alkali carbonates, alkaline earth carbonates, alkali hydrogencarbonates and
Erdalkalihydrogencarbonaten durchgeführt wird. Erdalkalihydrogencarbonaten is performed.
Verfahren gemäß einem der Ansprüche 1 bis 8, wobei das Verfahren in Gegenwart eines Lösungsmittels durchgeführt wird. A process according to any one of claims 1 to 8, wherein the process is carried out in the presence of a solvent.
10. Verfahren gemäß einem der Ansprüche 1 bis 9, wobei das Lösungsmittel ein unpolares Lösungsmittel ausgewählt aus der Gruppe bestehend aus Toluol, Xylol und Mesitylen ist.
A process according to any one of claims 1 to 9, wherein the solvent is a non-polar solvent selected from the group consisting of toluene, xylene and mesitylene.
1 1 . Verfahren gemäß Anspruch 9, wobei das Lösungsmittel ein polares Lösungsmittel, ausgewählt aus der Gruppe bestehend aus Wasser, Dimethylformamid, Formamid, tert-Amylalkohol und Acetonitril ist. 1 1. The method of claim 9, wherein the solvent is a polar solvent selected from the group consisting of water, dimethylformamide, formamide, tert-amyl alcohol and acetonitrile.
12. Verfahren gemäß einem der Ansprüche 1 bis 1 1 , wobei als Alkohol (AI) ein primärer oder sekundärer Monoalkohol und als Aminierungsmittel (Am) ein primäres Amin eingesetzt wird und als Amin (A) ein sekundäres Amin (As) erhalten wird. 12. The method according to any one of claims 1 to 1 1, wherein as alcohol (AI) a primary or secondary monoalcohol and as aminating agent (Am) a primary amine is used and as the amine (A) a secondary amine (As) is obtained.
13. Verfahren gemäß einem der Ansprüche 1 bis 1 1 , wobei als Alkohol (AI) ein primärer oder sekundärer Monoalkohol und als Aminierungsmittel (Am) ein sekundäres Amin eingesetzt wird und als Amin (A) ein tertiäres Amin (At) erhalten wird. 13. The method according to any one of claims 1 to 1 1, wherein as alcohol (AI) a primary or secondary monoalcohol and as aminating agent (Am) a secondary amine is used and as the amine (A) a tertiary amine (At) is obtained.
14. Verfahren gemäß einem der Ansprüche 1 bis 1 1 , wobei als Alkohol (AI) ein Diol mit zwei primären Hydroxylgruppen und als Aminierungsmittel (Am) ein primäres Amin eingesetzt wird und als Amin (A) ein tertiäres Amin (At) erhalten wird.
14. The method according to any one of claims 1 to 1 1, wherein as alcohol (AI) a diol having two primary hydroxyl groups and as aminating agent (Am) a primary amine is used and as amine (A) a tertiary amine (At) is obtained.
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---|---|---|---|---|
WO2017125358A1 (en) | 2016-01-20 | 2017-07-27 | Basf Se | Method for the homogeneously catalyzed production of mono-n-substituted piperazines |
CN111848412A (en) * | 2020-08-07 | 2020-10-30 | 赣南医学院 | Method for efficiently realizing N-alkylation reaction by using cycloiridium catalyst |
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Non-Patent Citations (13)
Title |
---|
AARON M. ROYER ET AL: "Coordination Chemistry of a Model for the GP Cofactor in the Hmd Hydrogenase: Hydrogen-Bonding and Hydrogen-Transfer Catalysis", INORGANIC CHEMISTRY, vol. 47, no. 2, 1 January 2008 (2008-01-01), pages 395 - 397, XP055074718, ISSN: 0020-1669, DOI: 10.1021/ic7018692 * |
ALEXANDER WETZEL ET AL: "Selective Alkylation of Amines with Alcohols by Cp*-Iridium(III) Half-Sandwich Complexes", ORGANIC LETTERS, vol. 15, no. 2, 18 January 2013 (2013-01-18), pages 266 - 269, XP055074752, ISSN: 1523-7060, DOI: 10.1021/ol303075h * |
DANIEL CARMONA ET AL: "Optically active pseudoctahedral rhodium(III), iridium(III), and ruthenium(II) complexes with [alpha]-amino acidato ligands. Crystal structures of RIrSCSN- and SIrSCSN-[(C5Me5)Ir(pro)Cl] . H2O (Hpro = l-proline)", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 396, no. 1, 1 October 1990 (1990-10-01), pages C17 - C21, XP055074727, ISSN: 0022-328X, DOI: 10.1016/0022-328X(90)85204-C * |
DANIELA KOCH ET AL: "N,O-Chelate complexes of Ru(II), Ir(III), Pd(II), Pt(II) and Cu(II) with tetrahydroisoquinolinic acid. Molecular structures of [(Et3P)(Cl)M(OOCCHCH2C6H4CH2NH)], M=Pd, Pt", INORGANICA CHIMICA ACTA, vol. 334, 1 May 2002 (2002-05-01), pages 365 - 370, XP055074724, ISSN: 0020-1693, DOI: 10.1016/S0020-1693(02)00862-9 * |
DAVID BALCELLS ET AL: "Mechanism of Homogeneous Iridium-Catalyzed Alkylation of Amines with Alcohols from a DFT Study", ORGANOMETALLICS, vol. 27, no. 11, 1 June 2008 (2008-06-01), pages 2529 - 2535, XP055074768, ISSN: 0276-7333, DOI: 10.1021/om800134d * |
DOUGLAS B. GROTJAHN ET AL: "Highly Stereoselective Formation of Cp*IrCl Complexes of N , N -Dimethylamino Acids", ORGANOMETALLICS, vol. 15, no. 4, 1 January 1996 (1996-01-01), pages 1230 - 1235, XP055074726, ISSN: 0276-7333, DOI: 10.1021/om9507890 * |
K. FUJITA; Y. ENOKI; R. YAMAGUCHI, TETRAHEDRON, vol. 64, 2008, pages 1943 - 1954 |
K. FUJITA; Z. LI; N. OZEKI; R. YAMAGUCHI, TETRAHEDRON LETT., vol. 44, 2003, pages 2687 - 2690 |
K.D. HENKEL: "Ullmann's Encyclopedia of Industrial Chemistry", 2005, WILEY-VCH VERLAG GMBH & CO. KGAA, DOI: 10.1002/14356007.B04_087, article "Reactor Types and Their Industrial Applications" |
O. SAIDI; A. J. BLACKER; M. M. FARAH; S. P. MARSDEN; J. M. J. WILLIAMS, CHEM. COMMUN., vol. 46, 2010, pages 1541 - 1543 |
R. KAWAHARA; K. FUJITA; R. YAMAGUCHI, ADV. SYNTH. CATAL., vol. 353, 2011, pages 1161 - 1168 |
R. KRÄMER; K POLBORN; H. WANJEK; I. ZAHN; W. BECK, CHEM. BER., vol. 123, 1990, pages 767 |
RYOKO KAWAHARA ET AL: "Multialkylation of Aqueous Ammonia with Alcohols Catalyzed by Water-Soluble Cp*Ir-Ammine Complexes", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 132, no. 43, 3 November 2010 (2010-11-03), pages 15108 - 15111, XP055074773, ISSN: 0002-7863, DOI: 10.1021/ja107274w * |
Cited By (3)
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WO2017125358A1 (en) | 2016-01-20 | 2017-07-27 | Basf Se | Method for the homogeneously catalyzed production of mono-n-substituted piperazines |
CN111848412A (en) * | 2020-08-07 | 2020-10-30 | 赣南医学院 | Method for efficiently realizing N-alkylation reaction by using cycloiridium catalyst |
CN111848412B (en) * | 2020-08-07 | 2023-05-12 | 赣南医学院 | Method for efficiently realizing N-alkylation reaction by using cycloiridium catalyst |
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