US3118825A - Electrochemical process for the production of organometallic compounds - Google Patents
Electrochemical process for the production of organometallic compounds Download PDFInfo
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- US3118825A US3118825A US35078A US3507860A US3118825A US 3118825 A US3118825 A US 3118825A US 35078 A US35078 A US 35078A US 3507860 A US3507860 A US 3507860A US 3118825 A US3118825 A US 3118825A
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- alkyl
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- lead
- ether
- lead compound
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- 238000000034 method Methods 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title description 8
- 150000002902 organometallic compounds Chemical class 0.000 title description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 66
- 239000002904 solvent Substances 0.000 claims description 31
- -1 MAGNESIUM HALIDE Chemical class 0.000 claims description 30
- 239000007818 Grignard reagent Substances 0.000 claims description 26
- 239000012071 phase Substances 0.000 claims description 24
- 239000000284 extract Substances 0.000 claims description 22
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 20
- 239000007791 liquid phase Substances 0.000 claims description 19
- 150000004795 grignard reagents Chemical class 0.000 claims description 13
- 150000001983 dialkylethers Chemical class 0.000 claims description 12
- 150000002611 lead compounds Chemical class 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 150000001350 alkyl halides Chemical class 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 72
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 46
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 32
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 22
- 238000005868 electrolysis reaction Methods 0.000 description 21
- 238000000605 extraction Methods 0.000 description 16
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- 238000004821 distillation Methods 0.000 description 15
- 229910001629 magnesium chloride Inorganic materials 0.000 description 11
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- 238000011084 recovery Methods 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000005292 vacuum distillation Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001256 steam distillation Methods 0.000 description 5
- XOOGZRUBTYCLHG-UHFFFAOYSA-N tetramethyllead Chemical compound C[Pb](C)(C)C XOOGZRUBTYCLHG-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 4
- 229960003750 ethyl chloride Drugs 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000004508 fractional distillation Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 2
- ZXHQLEQLZPJIFG-UHFFFAOYSA-N 1-ethoxyhexane Chemical group CCCCCCOCC ZXHQLEQLZPJIFG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 238000007700 distillative separation Methods 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FLAKGKCBSLMHQU-UHFFFAOYSA-N CC[Mg] Chemical compound CC[Mg] FLAKGKCBSLMHQU-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- OLOAJSHVLXNSQV-UHFFFAOYSA-N diethyl(dimethyl)plumbane Chemical compound CC[Pb](C)(C)CC OLOAJSHVLXNSQV-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 150000005218 dimethyl ethers Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- KHQJREYATBQBHY-UHFFFAOYSA-N ethyl(trimethyl)plumbane Chemical compound CC[Pb](C)(C)C KHQJREYATBQBHY-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical group [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 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
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/06—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals
- C07D295/067—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals with the ring nitrogen atoms and the substituents attached to the same carbon chain, which is not interrupted by carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/24—Oxygen atoms attached in position 8
- C07D215/26—Alcohols; Ethers thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/24—Oxygen atoms attached in position 8
- C07D215/26—Alcohols; Ethers thereof
- C07D215/28—Alcohols; Ethers thereof with halogen atoms or nitro radicals in positions 5, 6 or 7
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/04—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/32—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/24—Lead compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/13—Organo-metallic compounds
Definitions
- Tetraethyl lead and now tetramethyl lead, are important organometallic compounds of commerce. Many processes have been devised for their manufacture, although few have been commercially satisfactory.
- tetra-alkyl lead compounds such as tetraethyl lead may be prepared by electrolyzing an alkyl Grignard reagent, e.g., ethyl magnesium chloride, using a lead anode.
- alkyl Grignard reagent e.g., ethyl magnesium chloride
- lead anode alkyl groups on the Grignard reagent are transferred to the lead anode, forming tetra-alkyl lead and giving magnesium chloride as a by-product.
- This electrolytic process is vastly superior to purely chemical processes by reason of the low investment and reaction materials costs, particularly as applied to small plants.
- the electrolytic reaction mixture from electrolysis of an alkyl Grignard reagent with a lead anode and employing a dialkyl ether of an ethylene glycol having fewer than three ethylene groups in the glycol portion and having at least two carbon atoms in each alkyl group as Grignard reagent solvent is treated for recovery of the tetra-alkyl lead compound by (l) separating the reaction mixture into a first liquid phase containing unconverted Grignard reagent, a minor portion of the tetra-alkyl lead compound, magnesium halide and ether from a second liquid phase containing substantially only tetra-alkyl lead compound and ether, (2) extracting tetra-alkyl lead compound from the first liquid phase with a selective solvent chosen from the group consisting of paraffins and dialkyl ethers of ethylene glycols having fewer than three ethylene groups in the glycol portion, and mixtures thereof, (3) recovering tetra-alkyl lead compound from
- the foregoing recovery steps advantageously comprise distillation, preferably either vacuum or steam distillation to maintain relatively low temperatures. It will be particularly noted that at no stage of the inventive process is alkyl Grignard reagent heating in contact with the ether, thus minimizing or eliminating entirely any opportunities for decomposition of the latter by the former.
- the paraffin when the extracting solvent comprises a parafiin, the paraffin is an alkane or cycloalkane which boils below the boiling point of the particular tetra-alkyl lead compound produced.
- tetra-alltyl lead may be recovered from the extract by distillation.
- the extracting solvent'comprises a dialkyl ether of an ethylene glcol having fewer than three ethylene groups in the glycol portion tetra-alkyl lead recovery from the extract is readily accomplished by low temperature distillation, either under 3,113,825 Patented Jan. 21, 1964 vacuum or in the presence of steam.
- the identical solvent employed for the electrolysis may be the solvent for extraction, and accordingly the tetra-alkyl lead compound content of both the second liquid phase and the extract may be recovered simultaneously in the same distillation. This procedure has obvious advantages in terms of equipment savings.
- FlGURE 1 schematically shows a flow sheet of a process for preparing a tetra-alkyl lead compound by electrolyzing an alkyl Grignard reagent, recovering the tetra-alkyl lead compound by separating the electrolysis reaction mixture into two liquid phases, and extracting the tetra-alkyl lead compound from the phase containing unreacted Grignard reagent, tetra-alkyl lead compound, magnesium halide etherate, and ether with a paraflin solvent; and
- FIGURE 2 schematically shows a process wherein the electrolysis and separation steps are similar to those of FIGURE 1 but extraction is effected with a dialkyl ether of an ethylene glycol having fewer than three ethylene groups in the glycol portion.
- the electrolytic reaction may be represented by the formula:
- R represents an alkyl group, which may be the same or different alkyl groups in the formula, and where ethylene groups in the glycol portion and having at least two carbon atoms in each alkyl group.
- the suitable ethers have the formula, R-O(C H O) -R, wherein each R has at least two and advantageously not more than about ten carbon atoms in an alltyl group, and small 11 is one or two.
- the glycol ethers outside of the foregoing formula tend to form a magnesium halide etherate which precipitates out of the ether solution; glycol etherates within the formula defined above remain in solution and do not plug and foul equipment.
- Suitable glycol ethers are available commercially under the tradenames Cellosolves, wherein n is one, and Carbitols, wherein n is two. Examples of these Cellosolves and Carbitols together with their normal boiling points are diethyl Cellosolve (1l8l20 C.), dibutyl Cellosolve (204 C.), diethyl Carbitol (188 C.), dibutyl Carbitol (255 C.), and hexylethyl Carbitol (258 0.).
- the optimum glycol ether will depend on the particular tetra-alkyl lead compound being prepared; advantageously the glycol ether has a higher boiling point than the tetra-alkyl lead compound.
- tetramethyl lead boils at C.
- any of the Cellosolves may be employed
- tetraethyl lead boils at C. (with some decomposition) and consequently the higher boiling Cellosolves are preferred.
- glycol ethers may be chosen which boil at lower temperatures than the tetra-alkyl lead compound, in which event a distillative separation will result in the glycol ether be- '3 ing obtained as an overhead product while the tetra-alkyl lead compound is taken as a bottoms material.
- a special advantage of electrolytic tetra-alkyl lead processes is that they may be employed to manufacture a wide variety of tetra-alkyl lead compound.
- tetramethyl lead, tetraethyl lead, tetra-iso-butyl lead, dimethyl-diethyl lead, trimethyl-ethyl lead, and other allryl lead compounds may be prepared.
- tetraethyl and tetramethyl lead compounds are commercially desirable.
- the electrolyte before electrolysis commences advantageously contains the particular alkyl Grignard reagent at a concentration within the range of about 1.53.5 Normal, preferably within the range of about 22.5 Normal, and additionally contains excessive alkyl halide.
- the electrolysis may be conducted batchwise, continuously, or using any combination of modification of these methods. Temperatures in the electrolytic cells are advantageously within the range of about to about 100 C., preferably about -70 C., optimally about -60 C. Anode and cathode current densities are each desirably within the range of about 0.2 to about 25 amperes per hour per square foot. Cell pressures may range from atmospheric to high super-atmospheric-up to about 300 p.s.i.g. or even higher.
- Electrolysis is best continued until the alkyl Grignard reagent concentration is below about 1.0 Normal, and for economic reasons is optimally conducted until the concentration is within the range of about 0.2-0.5 Normal.
- the slight tetra-alkyl lead compound yield increase which may be obtained by continuing the electrolysis normally is outweighed by higher power requirements due to lower electrolyte conductivity at low Grignard concentrations.
- FIGURE 1 an embodiment of the invention employing a parafiin, hexane, to extract tetraethyl lead from a first liquid phase containing the tetraethyl lead, magnesium chloride etherate, unreacted ethyl magnesium chloride, and dibutyl Carbitol is shown.
- Ethyl Grignard is prepared and stored in source 11 at a concentration of 2.79 Normality in dibutyl Carbitol,
- the quantity of solution charged from source 11 via line 12 is 36.4 liters.
- Electrolysis is conducted in cell 19, containing a plurality of spaced plate electrodes.
- the anodes 16 are of lead, while the cathodes 17 are of a material which is inert when functioning as the anode, such as stainless steel.
- Ethyl chloride is added continuously during electrolysis via line 13 until a total of 5440 grams is added. All during the electrolytic reaction, the electrolyte is circulated via lines 21, 22, and 24 and pump 23 to maintain a continuously flowing electrolyte. If desired, heat exchange facilities may be installed in line 24 to permit removal of heat resulting from PR losses and from heat of reaction.
- the electrolyte is withdrawn via line 21 and transferred to surge drum 26.
- Grignard normality is approximately 0.54.
- the bottoms from surge drum 26 are pumped via line 29 to settling drum 31.
- the bottoms or ethyl-chloride-free electrolyte is permitted to separate into an upper first liquid phase 32 containing unconverted alkyl Grignard reagent, a minor portion of the tetraethyl lead, magnesium chloride etherate, and excess dibutyl Carbitol ether.
- the bottom layer 33 contains substantially only tetraethyl lead and ether, e.g., 1.73 molar with respect to tetraethyl lead, about 0.3 molar with respect to Grignard, and about 0.06 molar with respect to magnesium chloride etherate.
- the upper layer 32 contains only 0.271 mole per liter of tetraethyl lead with 0.69 mole per liter of Grignard, 2.59 moles per liter of total magnesium, and 4.53 moles per liter of total chloride.
- Lower layer 33 represents 25 volume percent of the electrolyte.
- the first or upper layer 32 contains the unreacted Grignard, the magnesium chloride etherate, a minor portion of the tetraethyl lead and ether, while it is the bottom or second layer which contains substantially only tetraethyl lead and the ether.
- the relative positions of these layers will depend on their relative densities and in turn will be dependent upon the initial composition of the electrolyte and on the extent of electrolysis, together with such other variables as temperatures, etc. Consequently, under some circumstances the densities and hence positions of the first and second layers may be reversed. This however offers no real problem and can be accommodated by simple reversal of the take-cit lines 34 and 41 from settling drum 31.
- the first layer is conducted via line 34 to extraction tower 36.
- This tower may be provided with a plurality of perforated plates to permit the first layer to receive intimate contact by the hexane as the former descends and the latter ascends. Countercurrent contact is most advantageous.
- tower 36 may be provided with doughnut battles and rotary agitators in each tower section separated by such bafiles. This permits even more efficient contact and extraction, and is especially useful since the denuded first layer becomes quite viscous.
- Conditions within tower 36, and the design of tower 36, are selected in view of operational and economic preferences to provide the most advantageous performance.
- the temperature may be varied widely, e.g., from about 10 to about 120 C., and the ratio of extracting solvent to first layer may vary from about 0.2:1 to about 20:1.
- the number of contact steps in tower 36 (or the height of tower 36 if a packed tower is employed) may also be selected in view of recognized engineering considerations.
- the extract phase leaving tower 36 is taken ed at the top via line 38 and passes to distillation tower 61.
- This extract phase is chiefly hexane and may contain from less than half to as much as percent or more of the tetraethyl lead originally present in the first layer admitted to extraction tower 36. It also contains a trace amount of unreacted Grignard and magnesium chloride etherate, but these ordinarily are not deleterious in the concentrations in which they are present.
- distillation tower 61 the lower boiling hexane is distilled overhead via vapor line 62, condensed by condenser 63, and sent to reflux drum 64.
- a portion of the hexane is returned via line 66 to distillation tower 61 to serve as tower reflux, while another portion is cycled via line 37 to extract tower 36 to repeat the tetraethyl lead extraction step.
- the bottoms from distillation tower 61 are largely tetraethyl lead with some unreacted alkyl Grignard reagent, magnesium chloride etherate, and perhaps some ether.
- This bottoms stream may either be withdrawn via line 68 and treated for tetraethyl lead recovery, as by fractional distillation, or else may be retained in the process as shown in FIGURE 1 by passing the bottoms via line 69 to fractional distillation column 42.
- Fractional distillation column 42 contains a plurality of distillation tray's or decks and may be supplied with tetraethyl lead and ether from lines 69 and 41, the latter furnishing the second layer resolved in separation drum 3].
- Column 42 may operate either by steam distillation or by vacuum distillation to resolve the tetraethyl leadether solution into its individual components. If vacuum distillation is employed, the column 42 is provided with a rcboiler and other conventional vacuum distillation auxiliaries, e.g., steam jets, etc. However, as shown in the drawing, distillation is advantageously conducted using live steam to obtain the separation. Vacuum distillation may be conducted at pressures from about 5 mm. mercury to about 700 mm. absolute pressure, while steam distillation may be conducted at an absolute pressure of from about 200 mm. pressure to about 50 p.s.i.g.
- the bottoms from tower 42. consists of moist ether and is conducted via line 51 to cooler 52 and thence to dropout drum 53. Here gross amounts of water are drained off via trap line 54, while the ether passes via line 56 to drier 57.
- Drier 57 contains a solid drying agent such as adsorbent alumina, silica gel, or a molecular sieve (zeolite) material.
- the dried ether taken through line 58 may be conducted via line 59' to the Grignard preparation facilities 11.
- FIGURE 2 an alternative system is shown which employs, in lieu of a paraffinic extracting solvent, a solvent comprising a dialkyl ether of an ethylene gly'col having fewer than three ethylene groups in the glycol portion.
- a solvent comprising a dialkyl ether of an ethylene gly'col having fewer than three ethylene groups in the glycol portion.
- suitable extracting solvent glycol ethers need not exclude the dimethyl ethers, although these are some what less preferred.
- the same glycol ether which is employed to eifect electrolysis is likewise employed for the extraction.
- the separation drum 31 corresponds to drum 31 of FIGURE 1, and all other analogous components are similarly numbered identically in the two figures.
- This tower similarly may be a multi-plate, an agitated, or a packed tower.
- a stream of dibutyl Carbitol is introduced via line 37; the
- proportion of extracting solvent to first phase may range from 0.2:1 to about 20: 1. It has been found that under some circumstances a small amount of extracting solvent will dissolve in the first liquid phase, but when the amount of additional solvent is increased, then virtually all of the original extracting solvent may be separated out as an immiscible phase.
- the extract consisting essentially of dibutyl Carbitol and tetraethyl lead leaves tower '36 via line 38 while denuded first liquid phase exhausts via line 39.
- This latter raffinate may be treated for additional tetraethyl lead and glycol ether recovery by hydrolyzing with an aqueous acid, the amount of acid being at least the quantity necessary to convert all of the magnesium to a magnesium salt.
- a hydrolyzed solution of this nature will form two phases; one containing the glycol ether and tetraethyl lead while the other contains aqueous magnesium salt. Hydrochloric acid is most convenient for the hydrolysis.
- the extract from the tower 36 leaving through line 38 is then conducted to a distillation tower 4-2, corresponding exactly to distillation tower 42 of FIGURE 1.
- the same tower may be employed for resolving the extract as is used for resolving the second liquid phase 33 in drum 31, and this embodiment is shown in FIGURE 2, wherein line 41 effects the introduction of second liquid phase 33.
- Distillation in tower 42 follows the procedures outlined in connection with FIGURE 1.
- Alternative glycol ethers which may be employed as extracting solvents include dimethyl Cellosolve, diethyl Cellosolve, dibutyl Cellosolve, dimethyl Carbitol, diethyl Carbitol, dibutyl Carbitol, and hexylethyl Carbitol.
- dried solvent from line 58 may be conducted both via line 59 to Grignard preparation facilities 11 and through line 37 to the extraction tower 36.
- Example I In this example a first liquid phase separated from a Grignard electrolysis is extracted with hexane. Extraction is effected batchwise, and although this is not the preferred technique it well illustrates the eifectiveness of the inventive process.
- Electrolysis is effected of a 2.79 Normal ethyl magnesium glycol solution in dibutyl Carbitol and containing approximately 10 percent excess ethyl chloride at all times.
- the final electrolyzed solution is approximately .69 Normal.
- This electrolyzed electrolyte is permitted to separate into two phases at 25 C. after excess ethyl chloride is removed.
- the first phase comprises 6.02 parts of a solution of unconverted Grignard reagent, tetraethyl lead, magnesium chloride etherate and excess ether.
- About 2.48 parts of the second liquid layer, comprising essentially only tetraethyl lead and ether is removed separately.
- a gram portion of the first or upper liquid layer is shaken in a separatory funnel with six portions of about 55 cc. each of hexane. Separation of phases is immediate at about 25 C. After each extraction the hexane upper phase is removed.
- the six extracts are combined and concentrated by distillation at atmospheric pressure. Analysis showed 14.2 grams of tetraethyl lead in the extract phase, with a trace of dibutyl Carbitol being present. The raflinate contains approximately 0.03 gram of TEL, representing a recovery of 98 percent.
- Example II In this example a portion of the electrolyzed electrolyte used for Example I is extracted with dibutyl Carbitol. Again, the extraction is batchwise, and the exceptional high extraction efliciency indicates the potential of a more efficient, continuous and countercurrent extraction.
- a 139 gram quantity of the first liquid phase is shaken with 31 grams of dibutyl Carbitol; the mixture becomes homogeneous.
- a second portion of dibutyl Cmbitol weighing 31 grams is added, and again the mixture remains homogeneous.
- Finally a 28 gram portion is added, and 65.3 grams of an upper extract phase separates out.
- This first extract contains 7.98 grams of tetraethyl lead.
- the rai'finate is extracted with 4-7 grams of dihutyl Carbitol, and 58.7 grams of extract containing 3.61 grams of tetraethyl lead is recovered.
- the total tetraethyl lead recovery is 13.56 grams. Analysis of the rafiinate shows that only 1.26 grams of tetraethyl lead is not recovered.
- the extract phase shows very little titratable alkalinity. Similarly, the titratable chloride ion is quite low, indicating that magnesium chloride and Grignard reagent are not appreciably extracted.
- the improved method of recovering the tetra-alkyl lead compound which comprises: separating the electrolyzed electrolyte into two immiscible liquid phases, the first phase containing unconverted Grignard reagent, a minor portion of the tetraalltyl lead compound, magnesium halide etherate, and ether, and the second phase containing substantially only tetra-alkyl lead compound and ether; extracting tetra-alkyl lead compound from said first phase with a solvent selected from the group consisting of paraifins, dialkyl ether
- dialltyl ether of an ethylene glycol in said electrolyte is dibutyl ether of diethyleue glycol.
- dialkyl ether of an ethylene glycol in said electrolyte is ethylhexyl ether of diethylene glycol.
- paratlin is a normally liquid paratfin boiling lower than the tetra-alltyl lead compound.
- said extracting solvent is a dialkyl ether of an ethylene glycol having fewer than 3 ethylene groups in the glycol portion.
- said extracting solvent is a dialkyl ether of an ethylene glycol having fewer than 3 ethylene roups in the glycol portion, and the tetraalkyl lead compound is recovered from the extract by vacuum distillation.
- said extracting solvent is a diallryl ether of an ethylene glycol having fewer than 3 ethylene groups in the glycol portion, and the tctra-alkyl lead compound is recovered from the extract by steam distillation.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Hydrogenated Pyridines (AREA)
- Plural Heterocyclic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Priority Applications (29)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL262356D NL262356A (fi) | 1960-03-15 | ||
LU39891D LU39891A1 (fi) | 1960-03-15 | ||
US35078A US3118825A (en) | 1960-03-15 | 1960-06-09 | Electrochemical process for the production of organometallic compounds |
US35441A US3155602A (en) | 1960-03-15 | 1960-06-13 | Preparation of organic lead compounds |
US67178A US3298939A (en) | 1960-03-15 | 1960-11-04 | Electrolytic preparation of organolead compounds |
US79845A US3164537A (en) | 1960-03-15 | 1960-12-30 | Recovery of tetraalkyl lead from electrolytic reaction mixtures |
ES0265759A ES265759A1 (es) | 1960-03-15 | 1961-03-14 | Un procedimiento para hacer un producto de plomo tetraalcohilo |
DEST17583A DE1157616B (de) | 1960-03-15 | 1961-03-15 | Verfahren zur Herstellung von Tetraalkylblei |
FR855672A FR1287026A (fr) | 1960-03-15 | 1961-03-15 | Perfectionnements apportés aux procédés pour la préparation de composés tétraalcoylés du plomb |
GB9445/61A GB984421A (en) | 1960-03-15 | 1961-03-15 | Electrolytic production of lead alkyl compounds |
US547780A US3584050A (en) | 1960-03-15 | 1966-05-05 | Nitrated aromatic alkamines |
IL25803A IL25803A (en) | 1960-03-15 | 1966-05-17 | Antimicrobial compositions containing nitrated alkamines and new nitrated alkamines |
SE6606793A SE375521B (fi) | 1960-03-15 | 1966-05-17 | |
SE7011413A SE379040B (fi) | 1960-03-15 | 1966-05-17 | |
GB22126/66A GB1142337A (en) | 1960-03-15 | 1966-05-18 | Amino nitroalkanes and their use as microbiocides |
NO163070A NO115641B (fi) | 1960-03-15 | 1966-05-18 | |
BE681371D BE681371A (fi) | 1960-03-15 | 1966-05-20 | |
AT481966A AT288340B (de) | 1960-03-15 | 1966-05-20 | Verfahren zur Herstellung von Aminonitroalkanen |
DE1620004A DE1620004C3 (de) | 1960-03-15 | 1966-05-20 | N-0-Phenyl-2-nitropropyi)-Piperazien, dessen Metallsalze und solche Verbindungen enthaltendes Schädlingsbekämpfungsmittel |
FI661331A FI51171C (fi) | 1960-03-15 | 1966-05-20 | Mikrobinvastaisina aineina käytettävät aminonitroalkaalit. |
AT1227268A AT314092B (de) | 1960-03-15 | 1966-05-20 | Verfahren zur Hemmung des Wachstums von niederen Tieren oder von Pflanzen und Mittel zu seiner Duchführung |
BR179699/66A BR6679699D0 (pt) | 1960-03-15 | 1966-05-20 | Processo para a preparacao de amino-mitroalcanos e composicoes pesticidas a base dos mesmos |
FR62411A FR1494137A (fr) | 1960-03-15 | 1966-05-20 | Composés et compositions antimicrobiens et pesticides, leurs procédés de fabrication et d'applications dans l'agriculture et l'industrie |
DK258666AA DK125262B (da) | 1960-03-15 | 1966-05-20 | Baktericid, fungicid, nematocid og algicid. |
NL6606997.A NL159975C (nl) | 1960-03-15 | 1966-05-20 | Werkwijze ter bereiding van tegen schadelijke organismen werkzame secundaire of tertiaire n-(2-nitroalkyl)aminen; werkwijze ter bereiding van tegen schadelijke organismen werkzame preparaten; de aldus verkregen gevormde voort- brengselen, alsmede werkwijze voor het bestrijden van microorganismen die slijmvorming en afbraak bij de papier- fabricage veroorzaken. |
IT11441/66A IT986753B (it) | 1960-03-15 | 1966-05-20 | Procedimento per la produzione di ammino nitroalcani utili quali fungicidi insetticidi e simili e prodotto ottenuto |
CH119169A CH534121A (de) | 1960-03-15 | 1966-05-23 | Verfahren zur Herstellung von mit einer Aminogruppe am B-C-Atom und mit einer Nitrogruppe am a-C-Atom substituierten Verbindungen |
CH119269A CH505551A (de) | 1960-03-15 | 1966-05-23 | Schädlingsbekämpfungsmittel |
CH739566A CH490318A (de) | 1960-03-15 | 1966-05-23 | Verfahren zur Herstellung von mit einer Aminogruppe am B-Kohlenstoffatom und mit einer Nitrogruppe am a-Kohlenstoffatom substituierten Verbindungen |
Applications Claiming Priority (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US1521160A | 1960-03-15 | 1960-03-15 | |
US35078A US3118825A (en) | 1960-03-15 | 1960-06-09 | Electrochemical process for the production of organometallic compounds |
US3544060A | 1960-06-13 | 1960-06-13 | |
US35441A US3155602A (en) | 1960-03-15 | 1960-06-13 | Preparation of organic lead compounds |
US67178A US3298939A (en) | 1960-03-15 | 1960-11-04 | Electrolytic preparation of organolead compounds |
US79845A US3164537A (en) | 1960-03-15 | 1960-12-30 | Recovery of tetraalkyl lead from electrolytic reaction mixtures |
US8526761A | 1961-01-27 | 1961-01-27 | |
US457802A US3399199A (en) | 1965-05-21 | 1965-05-21 | Nitroalkyl-piperazines |
US54778066A | 1966-05-05 | 1966-05-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3118825A true US3118825A (en) | 1964-01-21 |
Family
ID=27577975
Family Applications (5)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US35078A Expired - Lifetime US3118825A (en) | 1960-03-15 | 1960-06-09 | Electrochemical process for the production of organometallic compounds |
US35441A Expired - Lifetime US3155602A (en) | 1960-03-15 | 1960-06-13 | Preparation of organic lead compounds |
US67178A Expired - Lifetime US3298939A (en) | 1960-03-15 | 1960-11-04 | Electrolytic preparation of organolead compounds |
US79845A Expired - Lifetime US3164537A (en) | 1960-03-15 | 1960-12-30 | Recovery of tetraalkyl lead from electrolytic reaction mixtures |
US547780A Expired - Lifetime US3584050A (en) | 1960-03-15 | 1966-05-05 | Nitrated aromatic alkamines |
Family Applications After (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US35441A Expired - Lifetime US3155602A (en) | 1960-03-15 | 1960-06-13 | Preparation of organic lead compounds |
US67178A Expired - Lifetime US3298939A (en) | 1960-03-15 | 1960-11-04 | Electrolytic preparation of organolead compounds |
US79845A Expired - Lifetime US3164537A (en) | 1960-03-15 | 1960-12-30 | Recovery of tetraalkyl lead from electrolytic reaction mixtures |
US547780A Expired - Lifetime US3584050A (en) | 1960-03-15 | 1966-05-05 | Nitrated aromatic alkamines |
Country Status (15)
Country | Link |
---|---|
US (5) | US3118825A (fi) |
AT (2) | AT314092B (fi) |
BE (1) | BE681371A (fi) |
BR (1) | BR6679699D0 (fi) |
CH (3) | CH534121A (fi) |
DE (2) | DE1157616B (fi) |
DK (1) | DK125262B (fi) |
FI (1) | FI51171C (fi) |
GB (2) | GB984421A (fi) |
IL (1) | IL25803A (fi) |
IT (1) | IT986753B (fi) |
LU (1) | LU39891A1 (fi) |
NL (2) | NL159975C (fi) |
NO (1) | NO115641B (fi) |
SE (2) | SE379040B (fi) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3256161A (en) * | 1961-02-13 | 1966-06-14 | Nalco Chemical Co | Manufacture of tetramethyl lead |
US3372098A (en) * | 1965-01-21 | 1968-03-05 | Nalco Chemical Co | Process for recovering solvents from electrolytes |
US3380899A (en) * | 1964-10-16 | 1968-04-30 | Nalco Chemical Co | Electrolytic preparation and recovery of tetraalkyl lead compounds |
US3408273A (en) * | 1964-03-11 | 1968-10-29 | Nalco Chemical Co | Organic lead recovery from electrolytes by steam and azeotropic distillation |
US3458410A (en) * | 1965-07-30 | 1969-07-29 | Nalco Chemical Co | Purification of ethers |
US20140142332A1 (en) * | 2012-11-19 | 2014-05-22 | Technion Research & Development Foundation Limited | Process of preparing grignard reagent |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3312605A (en) * | 1961-02-13 | 1967-04-04 | Nalco Chemical Co | Preparation of organo metallic compounds |
DE1250441B (de) * | 1964-05-11 | 1967-09-21 | Ethyl Corporation, Baton Rouge, La. (V. St. A.) | Verfahren zur Herstellung von Alkyl-vinyl-bleiverbindungen |
US3359291A (en) * | 1964-10-05 | 1967-12-19 | Nalco Chemical Co | Purification of tetraalkyl lead |
US3522156A (en) * | 1964-10-21 | 1970-07-28 | Ethyl Corp | Production of hydrocarbon lead compounds |
BE671841A (fi) * | 1964-11-05 | |||
US3403983A (en) * | 1965-01-11 | 1968-10-01 | Mallinckrodt Chemical Works | Steam distillation of metal values in solution |
US3393137A (en) * | 1965-12-14 | 1968-07-16 | Nalco Chemical Co | Solvent recovery process |
US3409518A (en) * | 1966-01-06 | 1968-11-05 | Nalco Chemical Co | Organic halide recovery |
US3450608A (en) * | 1966-03-09 | 1969-06-17 | Nalco Chemical Co | Purification of ethers |
WO1990002782A1 (en) * | 1988-09-06 | 1990-03-22 | The Lubrizol Corporation | Nitro-groups containing amines, and fuels compositions containing same |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2944948A (en) * | 1956-02-06 | 1960-07-12 | Ethyl Corp | Method of purifying organometallic complexes and their use in the preparation of organolead compounds |
US3007858A (en) * | 1959-05-06 | 1961-11-07 | Nalco Chemical Co | Preparation of organo metallic compounds |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2535190A (en) * | 1949-04-01 | 1950-12-26 | Ethyl Corp | Manufacture of alkyllead compounds |
US2777867A (en) * | 1953-08-03 | 1957-01-15 | Ethyl Corp | Recovery of alkyllead compounds |
NL202273A (fi) * | 1954-11-26 | |||
BE569921A (fi) * | 1957-07-31 | |||
US2960450A (en) * | 1959-10-16 | 1960-11-15 | Ethyl Corp | Organo manganese compounds |
US3028319A (en) * | 1960-02-01 | 1962-04-03 | Ethyl Corp | Manufacture of magnesium organo compounds |
-
0
- NL NL262356D patent/NL262356A/xx unknown
- LU LU39891D patent/LU39891A1/xx unknown
-
1960
- 1960-06-09 US US35078A patent/US3118825A/en not_active Expired - Lifetime
- 1960-06-13 US US35441A patent/US3155602A/en not_active Expired - Lifetime
- 1960-11-04 US US67178A patent/US3298939A/en not_active Expired - Lifetime
- 1960-12-30 US US79845A patent/US3164537A/en not_active Expired - Lifetime
-
1961
- 1961-03-15 DE DEST17583A patent/DE1157616B/de active Pending
- 1961-03-15 GB GB9445/61A patent/GB984421A/en not_active Expired
-
1966
- 1966-05-05 US US547780A patent/US3584050A/en not_active Expired - Lifetime
- 1966-05-17 IL IL25803A patent/IL25803A/xx unknown
- 1966-05-17 SE SE7011413A patent/SE379040B/xx unknown
- 1966-05-17 SE SE6606793A patent/SE375521B/xx unknown
- 1966-05-18 GB GB22126/66A patent/GB1142337A/en not_active Expired
- 1966-05-18 NO NO163070A patent/NO115641B/no unknown
- 1966-05-20 NL NL6606997.A patent/NL159975C/xx not_active IP Right Cessation
- 1966-05-20 DK DK258666AA patent/DK125262B/da unknown
- 1966-05-20 AT AT1227268A patent/AT314092B/de not_active IP Right Cessation
- 1966-05-20 AT AT481966A patent/AT288340B/de not_active IP Right Cessation
- 1966-05-20 FI FI661331A patent/FI51171C/fi active
- 1966-05-20 BR BR179699/66A patent/BR6679699D0/pt unknown
- 1966-05-20 BE BE681371D patent/BE681371A/xx not_active IP Right Cessation
- 1966-05-20 DE DE1620004A patent/DE1620004C3/de not_active Expired
- 1966-05-20 IT IT11441/66A patent/IT986753B/it active
- 1966-05-23 CH CH119169A patent/CH534121A/de not_active IP Right Cessation
- 1966-05-23 CH CH739566A patent/CH490318A/de not_active IP Right Cessation
- 1966-05-23 CH CH119269A patent/CH505551A/de not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2944948A (en) * | 1956-02-06 | 1960-07-12 | Ethyl Corp | Method of purifying organometallic complexes and their use in the preparation of organolead compounds |
US3007858A (en) * | 1959-05-06 | 1961-11-07 | Nalco Chemical Co | Preparation of organo metallic compounds |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3256161A (en) * | 1961-02-13 | 1966-06-14 | Nalco Chemical Co | Manufacture of tetramethyl lead |
US3408273A (en) * | 1964-03-11 | 1968-10-29 | Nalco Chemical Co | Organic lead recovery from electrolytes by steam and azeotropic distillation |
US3380899A (en) * | 1964-10-16 | 1968-04-30 | Nalco Chemical Co | Electrolytic preparation and recovery of tetraalkyl lead compounds |
US3372098A (en) * | 1965-01-21 | 1968-03-05 | Nalco Chemical Co | Process for recovering solvents from electrolytes |
US3458410A (en) * | 1965-07-30 | 1969-07-29 | Nalco Chemical Co | Purification of ethers |
US20140142332A1 (en) * | 2012-11-19 | 2014-05-22 | Technion Research & Development Foundation Limited | Process of preparing grignard reagent |
US9145341B2 (en) * | 2012-11-19 | 2015-09-29 | Technion Research & Development Foundation Limited | Process of preparing Grignard reagent |
Also Published As
Publication number | Publication date |
---|---|
LU39891A1 (fi) | |
IL25803A (en) | 1971-05-26 |
DE1157616B (de) | 1963-11-21 |
SE375521B (fi) | 1975-04-21 |
IT986753B (it) | 1975-01-30 |
US3584050A (en) | 1971-06-08 |
GB1142337A (en) | 1969-02-05 |
US3155602A (en) | 1964-11-03 |
US3298939A (en) | 1967-01-17 |
CH534121A (de) | 1973-02-28 |
DE1620004C3 (de) | 1979-05-10 |
DK125262B (da) | 1973-01-29 |
SE379040B (fi) | 1975-09-22 |
NO115641B (fi) | 1968-11-04 |
NL159975B (nl) | 1979-04-17 |
AT288340B (de) | 1971-02-25 |
US3164537A (en) | 1965-01-05 |
NL6606997A (fi) | 1966-11-22 |
DE1620004B2 (de) | 1978-09-14 |
FI51171C (fi) | 1976-11-10 |
DE1620004A1 (de) | 1970-02-12 |
AT314092B (de) | 1974-03-25 |
FI51171B (fi) | 1976-08-02 |
NL159975C (nl) | 1979-09-17 |
CH490318A (de) | 1970-05-15 |
GB984421A (en) | 1965-02-24 |
BE681371A (fi) | 1966-11-21 |
BR6679699D0 (pt) | 1973-04-12 |
CH505551A (de) | 1971-04-15 |
NL262356A (fi) |
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