US2868698A - Manufacture of cyclopentadienyl manganese tricarbonyl compounds - Google Patents
Manufacture of cyclopentadienyl manganese tricarbonyl compounds Download PDFInfo
- Publication number
- US2868698A US2868698A US673765A US67376557A US2868698A US 2868698 A US2868698 A US 2868698A US 673765 A US673765 A US 673765A US 67376557 A US67376557 A US 67376557A US 2868698 A US2868698 A US 2868698A
- Authority
- US
- United States
- Prior art keywords
- manganese tricarbonyl
- distillation
- cyclopentadienyl
- product
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 title claims description 25
- DEIHRWXJCZMTHF-UHFFFAOYSA-N [Mn].[CH]1C=CC=C1 Chemical compound [Mn].[CH]1C=CC=C1 DEIHRWXJCZMTHF-UHFFFAOYSA-N 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title description 5
- 238000004821 distillation Methods 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 20
- -1 CYCLOPENTADIENE COMPOUND Chemical class 0.000 claims description 14
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 5
- 150000004760 silicates Chemical class 0.000 claims description 5
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 238000004326 stimulated echo acquisition mode for imaging Methods 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 12
- 239000011572 manganese Substances 0.000 description 12
- 235000002908 manganese Nutrition 0.000 description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 238000001256 steam distillation Methods 0.000 description 7
- ANHQLUBMNSSPBV-UHFFFAOYSA-N 4h-pyrido[3,2-b][1,4]oxazin-3-one Chemical group C1=CN=C2NC(=O)COC2=C1 ANHQLUBMNSSPBV-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 235000021313 oleic acid Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- LCGVCXIFXLGLHG-UHFFFAOYSA-N cyclopenta-1,3-diene;manganese(2+) Chemical compound [Mn+2].C1C=CC=[C-]1.C1C=CC=[C-]1 LCGVCXIFXLGLHG-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 235000019983 sodium metaphosphate Nutrition 0.000 description 3
- 235000019795 sodium metasilicate Nutrition 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- QZWPOKCFDVWLSU-UHFFFAOYSA-N CC1(C=CC=C1)[Mn]C1(C=CC=C1)C Chemical compound CC1(C=CC=C1)[Mn]C1(C=CC=C1)C QZWPOKCFDVWLSU-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical class NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001195 (9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid Substances 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- VAXCXSDAWONRLI-UHFFFAOYSA-N 2,3-dihydroxypropyl hydrogen sulfate Chemical compound OCC(O)COS(O)(=O)=O VAXCXSDAWONRLI-UHFFFAOYSA-N 0.000 description 1
- KEZYHIPQRGTUDU-UHFFFAOYSA-N 2-[dithiocarboxy(methyl)amino]acetic acid Chemical compound SC(=S)N(C)CC(O)=O KEZYHIPQRGTUDU-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- NMGMAOIYXASREJ-UHFFFAOYSA-N C(C)C1(C=CC=C1)[Mn]C1(C=CC=C1)CC Chemical compound C(C)C1(C=CC=C1)[Mn]C1(C=CC=C1)CC NMGMAOIYXASREJ-UHFFFAOYSA-N 0.000 description 1
- UEGKGEVCXOBKSV-UHFFFAOYSA-N C(C)[Mn]C1C=CC=C1 Chemical compound C(C)[Mn]C1C=CC=C1 UEGKGEVCXOBKSV-UHFFFAOYSA-N 0.000 description 1
- WAXPXRFFPKWFSX-UHFFFAOYSA-N C(CCCCCCC)[Mn]C1C=CC=C1 Chemical compound C(CCCCCCC)[Mn]C1C=CC=C1 WAXPXRFFPKWFSX-UHFFFAOYSA-N 0.000 description 1
- MBJZYLQGMODWJM-UHFFFAOYSA-N C1(=CC=CC=2C3=CC=CC=C3CC12)[Mn]C1=CC=CC=2C3=CC=CC=C3CC12 Chemical compound C1(=CC=CC=2C3=CC=CC=C3CC12)[Mn]C1=CC=CC=2C3=CC=CC=C3CC12 MBJZYLQGMODWJM-UHFFFAOYSA-N 0.000 description 1
- GAHCCFASRFYYAQ-UHFFFAOYSA-N C1(C=CC2=CC=CC=C12)[Mn] Chemical compound C1(C=CC2=CC=CC=C12)[Mn] GAHCCFASRFYYAQ-UHFFFAOYSA-N 0.000 description 1
- KDZSOJJFEINEDS-UHFFFAOYSA-N C[Mn]C1C=CC=C1 Chemical compound C[Mn]C1C=CC=C1 KDZSOJJFEINEDS-UHFFFAOYSA-N 0.000 description 1
- HPYIUKIBUJFXII-UHFFFAOYSA-N Cyclopentadienyl radical Chemical class [CH]1C=CC=C1 HPYIUKIBUJFXII-UHFFFAOYSA-N 0.000 description 1
- 101100055841 Danio rerio apoa1 gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000004686 pentahydrates Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- IYNDBHDAIOZDQC-UHFFFAOYSA-M sodium;1,2,3,4-tetrahydronaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])CCCC2=C1 IYNDBHDAIOZDQC-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000002023 wood Substances 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
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
Definitions
- This invention relates to. the manufacture of organo "'metal carbonyl compounds and more particularly to the separation and recovery of cyclopentadienyl manganese tricarbonyl compounds, and especially alkylcyclopentadienyl manganese tricarbonyls.
- Cyclopentadienyl manganese tricarbonyl compounds have been found to be exceptionally effective an-tiknocks for use in fuel, for spark plug'ignition internal combuspreciable'deposits on the engine piston, valves and spark plug surfaces and likewise are not abrasive to the engine parts as are characteristic of iron compounds.
- a preferred method of manufacture of these cycloreacting carbon monoxide with a bis-(cyclopentadienyl) manganese compound e. g. bis-(methylcyclopentadienyl) manganese.
- a bis-(cyclopentadienyl) manganese compound e. g. bis-(methylcyclopentadienyl) manganese.
- the othercyclopentadienyl radical is lost as byproduct, normally polymerizing to .a soft, sticky material. This byproduct causes difficulty in subsequent recovery of the cyclopentadienyl manganese tricarbonyl as hereinafter described.
- the bis(cyclopentadienyl)manganese compound is normallymade by--reaction of a cyclopentadienyl]sodium compound or other alkalimetal compound with a manganous chloride or other salt.
- Sodium chloride is formed as a byproduct, two moles per mole of the bis-manganese product.
- the carbon monoxide is normally added directly to this reaction product, forming a second product containing the desired cyclopentadienyl manganese tricarbonyl but also containing, frequently as the major constituent, impurities including the polymer, sodium salts, unreacted manganese salts and the like. These impurities interfere with complete recovery, e. g. distillation, of the desired product and, in addition, are extremely difficult to discharge from a steam still or other recovery equipment.
- :It is accordingly an object of this invention to provide an improved method for manufacture of cyclopentadienyl manganesetricarbonyl compounds. Another object is to provide; an improved method for the recovery and separation of'these compounds from a reaction product convtaining inorganic and polymeric impurities. A more specific object is to provide a simple and convenient United States Patent ally, when used alone, result in the formation of an emulpentadienyl manganese tricarbonyl compounds comprises objects and advantages of this invention will be apparent from the following description and appended claims.
- the alkali metal salts selected from the group consisting of silicates, phosphates, borates and carbonates when used in relatively low concentrations, have unexpected activity as steam distillation aids and are highly effective in maintaining the impurities in finely divided form such that essentially all of the desired cyclopentadienyl manganese tricarbonyl compound can be recovered from the crude reaction mass and such that the residue can be easily and completely discharged from the separation equipment as a fluid, easily handled slurry.
- dispersing agents, particularly of theanionic type additionally aid in efficient separation of the desired product while maintaining the residue in a fluid dischargeable state.
- the product can be recovered using steam distillation, without the many problems of agglomeration, low efliciency, etc.
- soaps and detergents are not equivalents to these alkali metal salts but, actusion which is extremely difficult to process, Likewise,
- inorganic and organic acids e. g. phosphoric or oleic acids
- sequestering agents in general, are not suitable for this invention.
- other inorganic salts such as sodium chloride are similarly ineffective.
- a preferred process of this invention comprises an initial distillation, either vacuum or under pressure, to remove the solvent from the crude reaction mass.
- the solvent-free reaction mass is then dispersed in water, containing from 1 to 10 percent of a steam distillation aid, as defined above, and thereafter steam distilled to separately recover the product.
- the impurities remain suspended in the aqueous phase.
- the solvent-free residue was then dispersed in an equal volume of water containing about 1 part of sodium metaphosphate (3 percent based on the weight of methylcyclopentadienyl manganese tricarbonyl). Thereafter, the solvent-free residue: was steam distilled using 40 p. s. i. g. steam and the temperature of the overhead was increased to between 100 to 105 C. at atmospheric pressure. The methylcyclopentadienyl manganese tricarbonyl product was'removed from the reaction mass as a water azeotrope and, upon separation of phases, about 34 parts of product were obtained.
- the distillation residue consisting primarily of metal salts and polymeric materials,v was finely divided and was readily discharged from the distillation equipment as a highly fluid aqueous slurry.
- the crude reaction product used in this example was prepared by reacting 3.36 parts of sodium metal with 14.26 parts of rnethylcyclopentadiene in 9.5 parts of diethylene glycol dirnethyl ether at a temperature of 110 C. After approximately one hour of agitation at this temperature, 9.15 parts of manganous chloride were added to the reaction mass and this mixture was thereafter agitated for approximately 1 /2 hours at 125 C. The reaction product was thereafter transferred to a pressure vessel wherein it was subjected to carbon monoxide pressure (500 p. s. i.) and this reaction mixture was vigorously agitated at 190 C. until the reaction was essentially complete. This crude reaction product, protected against exposure to air or moisture, was thereafter treated in accordance with the above procedure to recover the desired rnethylcyclopentadienyl manganese tricarbonyl.
- the manganese compound prepared as above is then subjected to fractionation and this purified product is thereafter blended with gasoline.
- Table I presents data showing the octane increase of a commercial gasoline having an initial boiling point of 94 F. and a final boiling point of 390 F.
- the antiknock value of the fuel as determined by the ratings are given in octane numbers for figures below 100 and in Army-Navy performance numbers for values above 100. The method of determining performance numbers is explained in the booklet Aviation Fuels and Their Effect on Engine Performance, NAVAER-06-5-501, USAF T. O. No. 06-554, published in 1951.
- Example I was repeated in a series of runs except that .no distillation aid was employed during the steam distillation.
- the solids agglomerated during the distillationsuch that only 60-80 percent of the product could be recovered.
- the distillate bottoms were large agglomerated masses which tenaciously stuck and were bonded to the vessel and had to be removed by scraping manually from the vessel walls.
- the material resembles an asphalt, varying from a tough pliable material to a hard brittle material in the several runs.
- Example III Example I was repeated except that sodium silicate (Na SiO' .9H O) was employed as the distillation aid. As in Example I, essentially complete recovery of the methylcyclopentadienyl product was obtained and there was noagglomeration or sticking of the distillate bottoms to the vessel walls. Instead, a finely divided slurry was discharged from" the" distillation still;
- sodium silicate Na SiO' .9H O
- Example IV Example I is repeated except that a composition containing about 28.8% trisodium phosphate, dodecahydrate, 34.8% tetrasodium pyrophosphate, 30.1% sodium metasilicate, pentahydrate, 2.2% sodium carbonate and 4.1% sodium stearate was employed as the distillation aid instead of' the sodium metaphosphate.
- 5 parts of the. distillation aid was employed for 321 parts of crude reaction mass (approximately 4% by weight, based on the weight of the rnethylcyclopentadienyl manganese tricarbonyl).
- the slurry obtained in this example was readily discharged from the steam still and could be easily handled byconventional process equipment.
- Example IV was repeated except that only 2.5 parts of the distillation aid was employed. Only a minor amount of agglomeration was obtained with this lower concentration.
- Example IV was repeated except that 10 parts of the distillation aid were employed with similar results.
- the distillation bottoms were not agglomerated and could be discharged from the steam still as a fine water slurry.
- Example VII ExampleI was repeated except that 5 parts of sodium carbonate (Na CO was employed with about 300 parts of crude reaction mass (about 4% based on the weight of methylcyclopentadienyl manganese tricarbonyl). No agglomeration of the distillation residue was encountered and the residue was readily slurried and discharged from the steam still.
- Na CO sodium carbonate
- Example VII was repeated except that 5 parts of sodium metasilicate was used with /2 part of Tide (a commercial detergent marketed by Proctor and Gamble).
- Example IX was repeated except that white soapwas used in place of the Tide. No agglomeration of the product residue was I encountered.
- Example I is repeated except that the crude reaction mass contained cyclopentadienyl manganese tricarbonyl, instead of the methyl substituted derivative. This crude reaction mass was prepared similarly to the product of Example I except that cyclopentadiene was employed instead of the methylcyclopentadiene.
- the present process is suitable for recovery of a wide variety of cyclopentadienyl manganese tricarbonyl compounds and is particularly desirable for recovery of such compounds having cyclopentadienyl radicals containing from 5 to 13 carbon atoms. These latter compounds have molecular weights up to about 315.
- cyclopentadienyl manganese tricarbonyl compounds which can be recovered in accordance with this invention are cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, idenyl manganese tricarbonyl, ethyl cyclopentadienyl manganese tricarbonyl, n-octyl cyclopentadienyl manganese tricarbonyl, phenyl methylcyclopentadienyl manganese tricarbonyl and the like.
- cyclopentadienyl manganese tricarbonyl compounds can be prepared from corresponding bis(cy clopentadienyl) alkali metal compounds by reaction with carbon monoxide.
- cyclopentadienyl manganese tricarbonyl is prepared by the reaction of carbon monoxide with bis(cyclopentadienyl) manganese.
- methylcyclopentadienyl manganese tricarbonyl is prepared by reacting carbon monoxide with bis(methylcyclopentadienyl) manganese.
- corresponding cyclopentadienyl manganese tricarbonyl compounds can be prepared from bis(ethyl cyclopentadienyl) manganese, bis(n-octyl cyclopentadienyl) manganese, 'bis(indenyl) manganese, bis(fluorenyl) manganese and the like.
- distillation aids suitable for this invention can be selected from the group consisting of alkali metal phosphates, silicates, carbonates and borates.
- suitable distillation aids are sodium, potassium and lithium metaphosphates, trisodium-, tripotassiumand trilithiumphosphates, the alkali metal pyrophosphates, such as tetrasodium pyrophosphate, sodium hexametaphosphate, sodium tripolyphosphate, the alkali metal metasilicates, such as sodium and potassium metasilicates, the alkali metal orthoand metasilicates, e. g. sodium orthosilicate and sodium metasilicate pentahydrate, the sesquisilicates, sodium and lithium metaborate, the polyborates, and the alkali metal vtetraborates, such as borax.
- distillation aids can be used in concentrations from about 1 to 10 percent, although a more preferred range is from 2 to 5 percent based upon the weight of the cyclopentadienyl manganese tricarbonyl compound in the crude reaction product. Lower concentrations can sometimes be employed although the results become somewhat inconsistent at the lower concentrations. Higher concentrations than 10 percent, while giving satisfactory operation, are usually unnecessary and uneconomic.
- the dispersing agents which are suitable in combination with the distillation aids are preferably of the anionic type and include soaps, and other products derived from the saponi'fication of fats, products obtained by direct sulfonation of fatty matter, products obtained by sulfonation of fatty esters, sulfonated aromatic hydrocarbons, sulfonated or chlorosulfonated paraflin hydrocarbons and sulfamides and sulfimides derived from paraflinic hydrocarbons.
- Suitable dispersing agents are soaps derived from oleic acid, caster oil, coconut oil; sulfonated glycerides and their fatty acids; sulfonated acids, such as oleic, linoleic and linolenic acids; sulfonated castor oil, sulfonated products of esterified castor oil e. g.
- sulfonated derivatives of fatty acids, mono-glycerides and mono-glycolides sodium alpha naphthalene monosulfonate, sodium tetrahydronaphthalene sulfonate, alkyl aryl sulfonates, such as sodium dodecyl benzene sulfonate, the alkali metal salts of octyldecylmethyl sulfamide; sodium lignosulfonate and the like.
- suitable dispersing agents are given in Encyclopedia of Surface Active Agents, Sisley and Wood, Chem. Publ. Co., N. Y. (1952).
- the concentration of dispersing agent employed can range from about 0.01 to 10 percent based upon the weight of the cyclopentadienyl manganese tricarbonyl compound in the crude reaction mixture. A more preferred concentration is from 1 to 5 percent. Greater quantities than these sometime results in emulsification, although the presence of the phosphates, silicates, borates and carbonates reduces this tendency. In fact, in the absence of the latter compounds, small quantities of the dispersing agent will normally result in emulsification, such as to make the distillation of the desired product almost impossible.
- the steam distillation can be carried out over a wide range of temperature and pressures and depends to a large extent on the cyclopentadienyl manganese tricarbonyl compound being distilled.
- the temperature of the distillation is usually the azeotropic temperature of the particular productand steam under the particular pressure conditions employed, normally from about 0 to C.
- the distillation is conducted at essentially atmospheric although pressures from sub-atmospheric up to about 1'0 atmospheres or higher can be employed.
- the crude reaction product should be protected from contact with air or moisture since materially greater difficulty is encountered in the distillation after prolonged exposure to either air or moisture. Normally, the reaction product is maintained under a inert atmosphere prior to distillation or the crude reaction mixture is fed directly to the distillation equipment in a closed system.
- the above cyclopentadienyl manganese tricarbonyl compounds can be prepared by a number of processes and, in general, are synthesized in three separate steps.
- An alkali metal (e. g. sodium, potassium or lithium) cyclopentadienyl compound is prepared by reaction of the corresponding alkali metal with the cyclopentadiene hydrocarbon in a suitable solvent, such as a hydrocarbon or ether, e. g. toluene, diethylene glycol diiri'c'thyl ether or tetrahydrofuran. This reaction is conducted with agi"-' tation at a temperature of from Ot'o 250 C.
- This'r'eaction mixture is then reacted with a manganous salt.
- Suitable manganous salts are halides, such as the chlorideor a bromide, manganous sulfate or organic salts, such as the acetate.
- this reaction is conducted in ether type solvents, such as those discussed above, at a temperature of 100 to 250 C., usually from 130 to 175 C.
- This second retraction product is then reacted with carbon monoxide usually at pressures of from 1-00 to 500 lbs./ sq. in., although both lower and higher pressures can be used.
- This carbonylation reaction is normally conducted at temperatures of from 150 to 250 C. using agitation.
- a process for producing cyclopentadienyl manganese tricarbonyl' compounds in which" a cyclopentadiene compound is reacted with an alkali 'metal, the reaction product is' thereafter reacted Witha -manganous salt and the product of the latter reaction is then reacted with carbon monoxide, in the presence of a solvent, the improvernent comprising steam distilling said cyclopentadienyl manganese tricarbonyl compound in the presence of from about l-lO percent by Weight, based on the Weight of said tricarbonyl compound, of a distillation aid selected from the group consisting of alkali metal phosphates, silicates, carbonates and borates.
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Description
MANUFACTURE OF CYCLOPENTADIENYL MAN- GANESE TRICARBONYL COMPOUNDS Hoyt J. Cragg, Baton Rouge, La., assignor to Ethyl Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application July 24, 1957 Serial No. 673,765
2 Claims. (Cl. 202-46) This invention relates to. the manufacture of organo "'metal carbonyl compounds and more particularly to the separation and recovery of cyclopentadienyl manganese tricarbonyl compounds, and especially alkylcyclopentadienyl manganese tricarbonyls.
' Cyclopentadienyl manganese tricarbonyl compounds have been found to be exceptionally effective an-tiknocks for use in fuel, for spark plug'ignition internal combuspreciable'deposits on the engine piston, valves and spark plug surfaces and likewise are not abrasive to the engine parts as are characteristic of iron compounds.
A preferred method of manufacture of these cycloreacting carbon monoxide with a bis-(cyclopentadienyl) manganese compound, e. g. bis-(methylcyclopentadienyl) manganese. In this reaction, only one of the two cyclopentadienyl radicals in the bis-compound is used in forming the product. The othercyclopentadienyl radical is lost as byproduct, normally polymerizing to .a soft, sticky material. This byproduct causes difficulty in subsequent recovery of the cyclopentadienyl manganese tricarbonyl as hereinafter described.
The bis(cyclopentadienyl)manganese compound is normallymade by--reaction of a cyclopentadienyl]sodium compound or other alkalimetal compound with a manganous chloride or other salt. Sodium chloride is formed as a byproduct, two moles per mole of the bis-manganese product. The carbon monoxide is normally added directly to this reaction product, forming a second product containing the desired cyclopentadienyl manganese tricarbonyl but also containing, frequently as the major constituent, impurities including the polymer, sodium salts, unreacted manganese salts and the like. These impurities interfere with complete recovery, e. g. distillation, of the desired product and, in addition, are extremely difficult to discharge from a steam still or other recovery equipment.
:It is accordingly an object of this invention to provide an improved method for manufacture of cyclopentadienyl manganesetricarbonyl compounds. Another object is to provide; an improved method for the recovery and separation of'these compounds from a reaction product convtaining inorganic and polymeric impurities. A more specific object is to provide a simple and convenient United States Patent ally, when used alone, result in the formation of an emulpentadienyl manganese tricarbonyl compounds comprises objects and advantages of this invention will be apparent from the following description and appended claims.
It has now been found that the alkali metal salts selected from the group consisting of silicates, phosphates, borates and carbonates, when used in relatively low concentrations, have unexpected activity as steam distillation aids and are highly effective in maintaining the impurities in finely divided form such that essentially all of the desired cyclopentadienyl manganese tricarbonyl compound can be recovered from the crude reaction mass and such that the residue can be easily and completely discharged from the separation equipment as a fluid, easily handled slurry. It has further been found that dispersing agents, particularly of theanionic type, additionally aid in efficient separation of the desired product while maintaining the residue in a fluid dischargeable state. Thus, the product can be recovered using steam distillation, without the many problems of agglomeration, low efliciency, etc.,
while at the same time obtaining the inherent advantages of excellent heat transfer, low temperature operation, rapid separation and an easily handled residue slurry.
The function of these alkali metal salts in improving product separation and maintaining the residue in a finely divided condition is not completely understood. However, it is known that the function is peculiar to these salts. Many somewhat similar materialsare completely ineffective for this purpose.
Thus, soaps and detergents are not equivalents to these alkali metal salts but, actusion which is extremely difficult to process, Likewise,
inorganic and organic acids, e. g. phosphoric or oleic acids, do not prevent agglomeration of the product residue. sequestering agents, in general, are not suitable for this invention. Also, other inorganic salts, such as sodium chloride are similarly ineffective.
More specifically, a preferred process of this invention comprises an initial distillation, either vacuum or under pressure, to remove the solvent from the crude reaction mass. The solvent-free reaction mass is then dispersed in water, containing from 1 to 10 percent of a steam distillation aid, as defined above, and thereafter steam distilled to separately recover the product. The impurities remain suspended in the aqueous phase. When solvents are used which have a boiling point higher than the cyclepentadienyl manganese tricarbonyl product, solvent distillation follows the steamdistillation.
- The following are typicalexamples of the present invention for the purpose of illustrating the beneficial characteristics of this invention. All units in the following examples are given in parts by weight.
EXAMPLE I A crude reaction product (IOOparts) containing about equal quantities of methylcyclopentadienyl manganese'tripressure of the'system'was reduced to 'abou't 2'to5 mni.
of mercury. Under these conditions, about 30 parts of solvent were recovered having a purity of about 95' percent. The solvent-free residue was then dispersed in an equal volume of water containing about 1 part of sodium metaphosphate (3 percent based on the weight of methylcyclopentadienyl manganese tricarbonyl). Thereafter, the solvent-free residue: was steam distilled using 40 p. s. i. g. steam and the temperature of the overhead was increased to between 100 to 105 C. at atmospheric pressure. The methylcyclopentadienyl manganese tricarbonyl product was'removed from the reaction mass as a water azeotrope and, upon separation of phases, about 34 parts of product were obtained. The distillation residue, consisting primarily of metal salts and polymeric materials,v was finely divided and was readily discharged from the distillation equipment as a highly fluid aqueous slurry.
The crude reaction product used in this example was prepared by reacting 3.36 parts of sodium metal with 14.26 parts of rnethylcyclopentadiene in 9.5 parts of diethylene glycol dirnethyl ether at a temperature of 110 C. After approximately one hour of agitation at this temperature, 9.15 parts of manganous chloride were added to the reaction mass and this mixture was thereafter agitated for approximately 1 /2 hours at 125 C. The reaction product was thereafter transferred to a pressure vessel wherein it was subjected to carbon monoxide pressure (500 p. s. i.) and this reaction mixture was vigorously agitated at 190 C. until the reaction was essentially complete. This crude reaction product, protected against exposure to air or moisture, was thereafter treated in accordance with the above procedure to recover the desired rnethylcyclopentadienyl manganese tricarbonyl.
The manganese compound prepared as above is then subjected to fractionation and this purified product is thereafter blended with gasoline. The following Table I presents data showing the octane increase of a commercial gasoline having an initial boiling point of 94 F. and a final boiling point of 390 F. The antiknock value of the fuel as determined by the ratings are given in octane numbers for figures below 100 and in Army-Navy performance numbers for values above 100. The method of determining performance numbers is explained in the booklet Aviation Fuels and Their Effect on Engine Performance, NAVAER-06-5-501, USAF T. O. No. 06-554, published in 1951.
Example I was repeated in a series of runs except that .no distillation aid was employed during the steam distillation. The solids agglomerated during the distillationsuch that only 60-80 percent of the product could be recovered. The distillate bottoms were large agglomerated masses which tenaciously stuck and were bonded to the vessel and had to be removed by scraping manually from the vessel walls. The material resembles an asphalt, varying from a tough pliable material to a hard brittle material in the several runs.
EXAMPLE III Example I was repeated except that sodium silicate (Na SiO' .9H O) was employed as the distillation aid. As in Example I, essentially complete recovery of the methylcyclopentadienyl product was obtained and there was noagglomeration or sticking of the distillate bottoms to the vessel walls. Instead, a finely divided slurry was discharged from" the" distillation still;
EXAMPLE IV Example I is repeated except that a composition containing about 28.8% trisodium phosphate, dodecahydrate, 34.8% tetrasodium pyrophosphate, 30.1% sodium metasilicate, pentahydrate, 2.2% sodium carbonate and 4.1% sodium stearate was employed as the distillation aid instead of' the sodium metaphosphate. In this example, 5 parts of the. distillation aid was employed for 321 parts of crude reaction mass (approximately 4% by weight, based on the weight of the rnethylcyclopentadienyl manganese tricarbonyl). The slurry obtained in this example was readily discharged from the steam still and could be easily handled byconventional process equipment.
EXAMPLE V Example IV was repeated except that only 2.5 parts of the distillation aid was employed. Only a minor amount of agglomeration was obtained with this lower concentration.
EXAMPLE VI Example IV was repeated except that 10 parts of the distillation aid were employed with similar results. The distillation bottoms were not agglomerated and could be discharged from the steam still as a fine water slurry.
EXAMPLE VII ExampleI was repeated except that 5 parts of sodium carbonate (Na CO was employed with about 300 parts of crude reaction mass (about 4% based on the weight of methylcyclopentadienyl manganese tricarbonyl). No agglomeration of the distillation residue was encountered and the residue was readily slurried and discharged from the steam still.
EXAMPLE VIII Example VII was repeated except that borax was employed and similar results were obtained.
EXAMPLE IX Example VII was repeated except that 5 parts of sodium metasilicate was used with /2 part of Tide (a commercial detergent marketed by Proctor and Gamble).
EXAMPLE X Example IX was repeated except that white soapwas used in place of the Tide. No agglomeration of the product residue was I encountered.
EXAMPLE PG Example VII was repeated except that 5parts of sodium metaphosphate was used with /2 part of the sodium salt of oleic acid. Equally good results were obtained.
EXAMPLE XII Example I is repeated except that the crude reaction mass contained cyclopentadienyl manganese tricarbonyl, instead of the methyl substituted derivative. This crude reaction mass was prepared similarly to the product of Example I except that cyclopentadiene was employed instead of the methylcyclopentadiene.
EXAMPLE XIII Example I is repeated except that the. crude reaction product contained indenyl manganese tricarbonyl instead of methylcyclopentadienyl manganese tricarbonyl. Similar results were obtained.
Thefollowing Table. 11 illustrates other embodiments of the present invention. In all instances, serious agglomeration ofthe reaction mass is avoided and the distillation residue can be: readily slurried and discharged from the steam still;
Table II Crude Reaction Mass Distillation Aid Inorg. Wt. Wt. Product Solvent Salt Metal Salt Per- Dispersant Per- 1 cent 1 cent 1 tetrahydrofuran LiCl NaiPzoa 2. dlethylene glycol dibutyl ether. K01 NaiPgoa 4. O sulfonated castor oil... 0. benzene-.. N 2.01 N21200:; 3.0 Ammonium ricmoleate... 0.7 toluene NaCl KP03 3. 0 lauryl alcohol sulfonate.... 0.2 diethylene glycol diethyl ether. KCl LIP O 3. 5 fatty amide sulfonate 0. 9 tetraethylene glycol dimethyl NaGl K O 2. 5 sodium salt of butyl 1. 5
ether. rieinoleate. cyclohexylamine NaOl Nag]? O4 4. 0 stearo glycerol sulfate.... 0. 6 diethylene glycol dimethyl N 9.01 NaPOi 2. 8 sodium alkyl naphthalene 4. 0
ether. sulfonate (Alkoterge). .do N aOl Na? 03 3. 0 sulfonation product of wax 1. 2
residues. MMT... do. NaOl N aPOa 4. 5 sodium ligno sult'onate... 1. 0
1 Based on the Weight of cyclopentadienyl manganese trllcarbonyl product.
MMT-methylcyclopentadlenyl manganese trlcarbony GMT-cyclopentadienyl manganese tricarbonyl. EMT-ethylcyclopentadienyl manganese tricarbonyl. IMT-indenyl manganese tricarbonyl.
The present process is suitable for recovery of a wide variety of cyclopentadienyl manganese tricarbonyl compounds and is particularly desirable for recovery of such compounds having cyclopentadienyl radicals containing from 5 to 13 carbon atoms. These latter compounds have molecular weights up to about 315. Typical examples of cyclopentadienyl manganese tricarbonyl compounds which can be recovered in accordance with this invention are cyclopentadienyl manganese tricarbonyl, methylcyclopentadienyl manganese tricarbonyl, idenyl manganese tricarbonyl, ethyl cyclopentadienyl manganese tricarbonyl, n-octyl cyclopentadienyl manganese tricarbonyl, phenyl methylcyclopentadienyl manganese tricarbonyl and the like.
The above cyclopentadienyl manganese tricarbonyl compounds can be prepared from corresponding bis(cy clopentadienyl) alkali metal compounds by reaction with carbon monoxide. For example, cyclopentadienyl manganese tricarbonyl is prepared by the reaction of carbon monoxide with bis(cyclopentadienyl) manganese. Likewise, methylcyclopentadienyl manganese tricarbonyl is prepared by reacting carbon monoxide with bis(methylcyclopentadienyl) manganese. Thus, corresponding cyclopentadienyl manganese tricarbonyl compounds can be prepared from bis(ethyl cyclopentadienyl) manganese, bis(n-octyl cyclopentadienyl) manganese, 'bis(indenyl) manganese, bis(fluorenyl) manganese and the like.
The distillation aids suitable for this invention, as noted above, can be selected from the group consisting of alkali metal phosphates, silicates, carbonates and borates. Typical examples of suitable distillation aids are sodium, potassium and lithium metaphosphates, trisodium-, tripotassiumand trilithiumphosphates, the alkali metal pyrophosphates, such as tetrasodium pyrophosphate, sodium hexametaphosphate, sodium tripolyphosphate, the alkali metal metasilicates, such as sodium and potassium metasilicates, the alkali metal orthoand metasilicates, e. g. sodium orthosilicate and sodium metasilicate pentahydrate, the sesquisilicates, sodium and lithium metaborate, the polyborates, and the alkali metal vtetraborates, such as borax.
The above distillation aids can be used in concentrations from about 1 to 10 percent, although a more preferred range is from 2 to 5 percent based upon the weight of the cyclopentadienyl manganese tricarbonyl compound in the crude reaction product. Lower concentrations can sometimes be employed although the results become somewhat inconsistent at the lower concentrations. Higher concentrations than 10 percent, while giving satisfactory operation, are usually unnecessary and uneconomic.
The dispersing agents which are suitable in combination with the distillation aids are preferably of the anionic type and include soaps, and other products derived from the saponi'fication of fats, products obtained by direct sulfonation of fatty matter, products obtained by sulfonation of fatty esters, sulfonated aromatic hydrocarbons, sulfonated or chlorosulfonated paraflin hydrocarbons and sulfamides and sulfimides derived from paraflinic hydrocarbons. Typical examples of suitable dispersing agents are soaps derived from oleic acid, caster oil, coconut oil; sulfonated glycerides and their fatty acids; sulfonated acids, such as oleic, linoleic and linolenic acids; sulfonated castor oil, sulfonated products of esterified castor oil e. g. with butyl alcohol; sulfonated derivatives of fatty acids, mono-glycerides and mono-glycolides, sodium alpha naphthalene monosulfonate, sodium tetrahydronaphthalene sulfonate, alkyl aryl sulfonates, such as sodium dodecyl benzene sulfonate, the alkali metal salts of octyldecylmethyl sulfamide; sodium lignosulfonate and the like. Many other examples of suitable dispersing agents are given in Encyclopedia of Surface Active Agents, Sisley and Wood, Chem. Publ. Co., N. Y. (1952).
The concentration of dispersing agent employed can range from about 0.01 to 10 percent based upon the weight of the cyclopentadienyl manganese tricarbonyl compound in the crude reaction mixture. A more preferred concentration is from 1 to 5 percent. Greater quantities than these sometime results in emulsification, although the presence of the phosphates, silicates, borates and carbonates reduces this tendency. In fact, in the absence of the latter compounds, small quantities of the dispersing agent will normally result in emulsification, such as to make the distillation of the desired product almost impossible.
The steam distillation can be carried out over a wide range of temperature and pressures and depends to a large extent on the cyclopentadienyl manganese tricarbonyl compound being distilled. The temperature of the distillation is usually the azeotropic temperature of the particular productand steam under the particular pressure conditions employed, normally from about 0 to C. Usually the distillation is conducted at essentially atmospheric although pressures from sub-atmospheric up to about 1'0 atmospheres or higher can be employed.
The crude reaction product should be protected from contact with air or moisture since materially greater difficulty is encountered in the distillation after prolonged exposure to either air or moisture. Normally, the reaction product is maintained under a inert atmosphere prior to distillation or the crude reaction mixture is fed directly to the distillation equipment in a closed system.
The above cyclopentadienyl manganese tricarbonyl compounds can be prepared by a number of processes and, in general, are synthesized in three separate steps. An alkali metal (e. g. sodium, potassium or lithium) cyclopentadienyl compound is prepared by reaction of the corresponding alkali metal with the cyclopentadiene hydrocarbon in a suitable solvent, such as a hydrocarbon or ether, e. g. toluene, diethylene glycol diiri'c'thyl ether or tetrahydrofuran. This reaction is conducted with agi"-' tation at a temperature of from Ot'o 250 C. preferably above 100 C., using either the cyclopentadiene monomer or dimer. Other suitable methods are disclosed in British 763,047 and U. S. 2,777,887. This'r'eaction mixture is then reacted with a manganous salt. Suitable manganous salts are halides, such as the chlorideor a bromide, manganous sulfate or organic salts, such as the acetate. In general, this reaction is conducted in ether type solvents, such as those discussed above, at a temperature of 100 to 250 C., usually from 130 to 175 C. This second retraction product is then reacted with carbon monoxide usually at pressures of from 1-00 to 500 lbs./ sq. in., although both lower and higher pressures can be used. This carbonylation reaction is normally conducted at temperatures of from 150 to 250 C. using agitation.
I claim:
1. In aprocess for producing cyclopentadienyl manganese tricarbonyl' compounds in which" a cyclopentadiene compound is reacted with an alkali 'metal, the reaction product is' thereafter reacted Witha -manganous salt and the product of the latter reaction is then reacted with carbon monoxide, in the presence of a solvent, the improvernent comprising steam distilling said cyclopentadienyl manganese tricarbonyl compound in the presence of from about l-lO percent by Weight, based on the Weight of said tricarbonyl compound, of a distillation aid selected from the group consisting of alkali metal phosphates, silicates, carbonates and borates.
2. The process of claim 1 wherein the steam distillation is conducted inth'e additional presence of from about 0.1 to 10 percent of a dispersingagent.
No references cited.
Claims (1)
1. IN A PROCESS FOR PRODUCING CYCLOPENTADIENYL MANGANESE TRICARBONYL COMPOUNDS IN WHICH A CYCLOPENTADIENE COMPOUND IS REACTED WITH AN ALKALI METAL, THE REACTION PRODUCT IS THEREAFTER REACTED WITH A MANGANOUS SALT AND THE PRODUCT OF THE LATTER REACTION IS THEN REACTED WITH CARBON MONOXIDE, IN THE PRESENCE OF A SOLVENT, THE IMPROVEMENT COMPRISING STEAM DISTILLING SAID CYCLOPENTADIENYL MANGANESE TRICARBONYL COMPOUND IN THE PRESENCE OF FROM ABOUT 1-10 PERCENT BY WEIGHT, BASED ON THE WEIGHT OF SAID TRICARBONYL COMPOUND, OF A DISTILLATION AID SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL PHOSPHATES, SILICATES, CARBONATES AND BORATES.
Priority Applications (1)
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US673765A US2868698A (en) | 1957-07-24 | 1957-07-24 | Manufacture of cyclopentadienyl manganese tricarbonyl compounds |
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Application Number | Priority Date | Filing Date | Title |
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US673765A US2868698A (en) | 1957-07-24 | 1957-07-24 | Manufacture of cyclopentadienyl manganese tricarbonyl compounds |
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US2868698A true US2868698A (en) | 1959-01-13 |
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US673765A Expired - Lifetime US2868698A (en) | 1957-07-24 | 1957-07-24 | Manufacture of cyclopentadienyl manganese tricarbonyl compounds |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4946975A (en) * | 1990-01-12 | 1990-08-07 | Ethyl Corporation | Process for making methylcyclopentadienyl manganese tricarbonyl compounds |
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1957
- 1957-07-24 US US673765A patent/US2868698A/en not_active Expired - Lifetime
Non-Patent Citations (1)
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None * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4946975A (en) * | 1990-01-12 | 1990-08-07 | Ethyl Corporation | Process for making methylcyclopentadienyl manganese tricarbonyl compounds |
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