US3155602A - Preparation of organic lead compounds - Google Patents

Preparation of organic lead compounds Download PDF

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Publication number
US3155602A
US3155602A US35441A US3544160A US3155602A US 3155602 A US3155602 A US 3155602A US 35441 A US35441 A US 35441A US 3544160 A US3544160 A US 3544160A US 3155602 A US3155602 A US 3155602A
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lead
alkyl
tetrahydrofuran
ether
electrolyte
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US35441A
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Linsk Jack
Evan A Mayerle
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Standard Oil Co
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Standard Oil Co
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Priority to NL262356D priority Critical patent/NL262356A/xx
Priority to LU39891D priority patent/LU39891A1/xx
Priority to US35078A priority patent/US3118825A/en
Application filed by Standard Oil Co filed Critical Standard Oil Co
Priority to US35441A priority patent/US3155602A/en
Priority to US67178A priority patent/US3298939A/en
Priority to US79845A priority patent/US3164537A/en
Priority to ES0265759A priority patent/ES265759A1/en
Priority to DEST17583A priority patent/DE1157616B/en
Priority to FR855672A priority patent/FR1287026A/en
Priority to GB9445/61A priority patent/GB984421A/en
Publication of US3155602A publication Critical patent/US3155602A/en
Application granted granted Critical
Priority claimed from US457802A external-priority patent/US3399199A/en
Priority to US547780A priority patent/US3584050A/en
Priority to SE6606793A priority patent/SE375521B/xx
Priority to SE7011413A priority patent/SE379040B/xx
Priority to IL25803A priority patent/IL25803A/en
Priority to NO163070A priority patent/NO115641B/no
Priority to GB22126/66A priority patent/GB1142337A/en
Priority to FI661331A priority patent/FI51171C/en
Priority to BR179699/66A priority patent/BR6679699D0/en
Priority to NL6606997.A priority patent/NL159975C/en
Priority to AT481966A priority patent/AT288340B/en
Priority to IT11441/66A priority patent/IT986753B/en
Priority to FR62411A priority patent/FR1494137A/en
Priority to DE1620004A priority patent/DE1620004C3/en
Priority to AT1227268A priority patent/AT314092B/en
Priority to BE681371D priority patent/BE681371A/xx
Priority to DK258666AA priority patent/DK125262B/en
Priority to CH119169A priority patent/CH534121A/en
Priority to CH739566A priority patent/CH490318A/en
Priority to CH119269A priority patent/CH505551A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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

  • This invention relates to organometallic compounds and more particularly concerns improvements in an electrolytic process for preparing tetra-alkyl lead compounds such as tetnaethyl lead or tetramethyl lead.
  • Tetraethyl lead, and now tetrarnethyl lead, are important organometallic compounds of commerce. It has heretofore been discovered that tetra-alkyl lead compounds such as these may be prepared by electrolyzing an alkyl Grignard reagent, e.g. ethyl magnesium chloride, using a lead anode. By this procedure, alkyl groups on the Grignard reagent are transferred to the lead anode, forming tetra-alkyl lead and giving magnesium chloride as a byproduct. This electrolytic process is vastly superior to purely chemical processes by reason of the low investment and raw materials costs.
  • alkyl Grignard reagent e.g. ethyl magnesium chloride
  • electrolysis of an electrolyte comprising an alkyl Grignard reagent, excess alkyl halide, and an ether, with a lead anode, is effected with an ether mixture comprising, in conjoint presence, a dialkyl ether of an ethylene glycol having at least two carbon atoms in each alkyl group and not more than two ethylene groups in the glycol portion, and tetrahydrofuran.
  • the invention is based in part on the discovery that tetrahydrofuran markedly increases the conductivity of Grignard-containing electrolyte, frequently by a factor of 3 to 5 fold.
  • the inventive ether mixture preferably comprises from about 98 to about 40 percent by weight of a dialkyl ether of an ethylene glycol and from about 2 to about 60 percent by weight of tetrahydrofuran.
  • a more optimum range is from about 90 to about 60% of dialkyl ether of an ethylene glycol and about -40 percent by weight of tetrahydrofuran. It has been found that, under some conditions, too high a tetrahydrofuran concentration may lead to the deposition of solid magnesium halide etherate which may make electrolysis rather diflicult, and accordingly it is desirable but not essential to operate within the foregoing broad range.
  • the dialkyl ethers of ethylene glycols employed herein are the dialkyl ethers of ethylene glycols having at least two carbon atoms in each alkyl group and not more than two ethylene groups in the glycol portion.
  • the ethers have the formula R-O-(C H O) R, where the R's are the same or different alkyl groups, each having at least twoand suitably up to about 12 carbon atoms per group.
  • n is either one or two.
  • Ethers outside of the foregoing definition tend to form a magnesium chloride etherate which precipitates from the electrolyte, thereby fouling equipment. Examples of Patented Nov.
  • suitable ethers for use herein include the Carbitols, wherein n is one, and the Cellosolves, wherein n is two. Specific ethers are diethyl Cellosolve, dibutyl Cellosolve, diethyl Carbitol, dibutyl Carbitol, and diethyl hexyl Carbitol.
  • the alkyl Grignard reagents are chosen to produce the desired tetra-alkyl lead compound.
  • an ethyl Grignard will affordtetraethyl lead while a methyl Grignard will produce tetramethyl lead.
  • the alkyl lead compounds having from 1 to about 4 carbon atoms per alkyl group are most effectively produced by the electrolytic process.
  • mixed Grignard reagents such as a mixture of ethyl Grignard and methyl Grignard
  • a mixed tetra-alkyl compound may be prepared; thus dimethyl diethyl lead may be obtained.
  • the halide portion of the alkyl Grignard reagent may be the chloride, the bromide, or, less desirably, the iodide.
  • alkyl halide concentrations of, say l-50 weight percent of the total electrolyte, react with magnesium metal which will otherwise plate out on the cathode and short the electrodes; it assists in maintaining a high level of electrolyte conductivity; it reduces side reactions; and it appears to provide a current efiiciency well in excess of the theoretical.
  • this perhaps is due to the formation of a dialkyl lead compound electrolytically, which may then react with alkyl Grignard reagent chemically to form tetralykyl lead, requiring only two faradays per mol.
  • the alkyl halide will correspond with the alkyl Grignard reagent; for exampe, ethyl chloride would normally be used with ethyl magnesium chloride.
  • Grignard reagents are well known and no discussion of their preparation is necessary.
  • Conditions in the electrolytic cell advantageously include a temperature within the range of about 20 to about C., preferably 40-70 C., and optimally about 45-60" C.
  • Anode and cathode current densities are each preferably within the range of about 0.2 to about 35 amperes per square foot.
  • Cell pressures may range from atmospheric to high superatmospheric-up to 300 p.s.i.g. or even higher.
  • :Alkyl Grignard concentrations before the onset of electrolysis are advantageously within the range of about 1.5-3.5 Normal, and eletrolysis maybe continued until the electrolyte contains as little as 0.3 Normal Grignard, or even less.
  • a 1.5 Normal ethyl magnesium chloride solution containing 10.8 weight percent tetrahydrofuran has a specific resistance of 6,700 ohm-centimeters
  • a' 21.6% tetrahydrofuran solution has a specific resistance of 3,600 ohm-centimeters.
  • Example I furan to produce tetramethyl lead. e
  • an electrolytic cell having three lead electrodes spaced about one-eighth inch apart and each being a two inch by 3 inch rectangle, 190 grams of a 2.0 Normal methyl magnesium chloride solution in dibutyl Carbitol is added. The outer plates are connected together to serve as a cathode. Cell characteristics are determined by applying progressively increasing voltages across the electrodes and measuring the amperages.
  • Unreacted methyl chloride is bled 01? and the cell contents are transferred to a flask.
  • Two liquid layers separate out, a clear upper layer containing tetrahydrofuran, dibutyl Carbitol, and tetramethyl lead with only a trace of Grignard (0.01 Normal), and a dark viscous lower layer containing residual Grignard reagent, magnesium chloride etherate, and some tetramethyl lead, tetrahydrofuran, and dibutyl Carbitol.
  • the upper phase contains 19 weight percent tetramethyl lead and represents roughly 50% of the total tetramethyl lead produced.
  • Both phases are hydrolyzed with ice and aqueous hydrochloric acid.
  • the organic phase is steam distilled at about 100 C.
  • the overhead distillate contains tetrahydrofuran as well as tetramethyl lead, and is repeatedly water Washed to remove the tetrahydrofuran.
  • Tetramethyl lead is recovered in a yield of 19.1 grams, and remains water white after exposure to light for several weeks.
  • Example II In this example a methyl Grignard reagent is electrolyzed with an ether mixture containing 40%' tetrahydrofuran and 60% dibutyl Carbitol by weight.
  • the cell contents are then hydrolyzed with saturated aqueous ammonium chloride solution and the liquid phase which separates out is steam distilled.
  • the overhead mixture of tetramethyl lead and tetrahydrofuran is washed repeatedly with aqueous sodium chloride.
  • Tetramethyl lead is recovered in a yield of 24.9 grams. By gas chromatography the product is shown to contain more than 95% tetramethyl lead by weight.
  • a process for preparing a tetra-alkyl lead compound by electrolyzing an electrolyte comprising an alkyl Grignard reagent, excess alkyl halide, and an ether, with a lead anode the improvement characterized by superior electrolyte conductivity which comprises effecting said electrolysis in the presence of an ether mixture comprising, in conjoint presence, from about 98 to about 40% by Weight of a dialkyl ether of an ethylene glycol having at least two carbon atoms in each alkyl group and not more than two ethylene groups in the glycol portion, and from about 2 to about 60% by weight of tetrahydrofuran.
  • said ether mixture comprises from about to about 60% of said dialkyl ether ⁇ of an ethylene glycol and from about 10 to about 40% of tetrahydrofuran.
  • dialkyl ether of an ethylene glycol is dibutyl ether of diethylene glycol.
  • dialkyl ether of an ethylene glycol is ethyl hexyl ether of diethylene glycol.

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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)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Hydrogenated Pyridines (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

United States Patent 3,155,602 PREPARATION OF ORGANIC LEAD COMPOUNDS .laclr Linsk, Highland, Ind., and Evan A. Mayerle, Lansing, IiL, assignors to Standard Oil Company, Chicago,
Ill., a corporation of Indiana No Drawing. Filed June 13, 1960, Ser. No. 35,441
6 Claims. (Cl. 204-59) This invention relates to organometallic compounds and more particularly concerns improvements in an electrolytic process for preparing tetra-alkyl lead compounds such as tetnaethyl lead or tetramethyl lead.
Tetraethyl lead, and now tetrarnethyl lead, are important organometallic compounds of commerce. It has heretofore been discovered that tetra-alkyl lead compounds such as these may be prepared by electrolyzing an alkyl Grignard reagent, e.g. ethyl magnesium chloride, using a lead anode. By this procedure, alkyl groups on the Grignard reagent are transferred to the lead anode, forming tetra-alkyl lead and giving magnesium chloride as a byproduct. This electrolytic process is vastly superior to purely chemical processes by reason of the low investment and raw materials costs.
Unfortunately, certain processing difficulties are inherent in this electrolytic process. One of the most serious of these is the fact that electrolytic conductivity decreases substantially during electrolysis, often dropping to less than half of the original value. Decreased conductivity, or its correlative opposite, higher resistance, lowers the obtainable current density at constant voltage. Not only does this decrease electrolytic cell capacity but it imposes higher power requirements and also produces undesirable heating effects due to PR loss. It is accordingly a major object of the present invention to provide an improved electrolytic tetra-alkyl lead process wherein electrolyte conductivity is maintained at a high level.
Briefly, according to the invention, electrolysis of an electrolyte comprising an alkyl Grignard reagent, excess alkyl halide, and an ether, with a lead anode, is effected with an ether mixture comprising, in conjoint presence, a dialkyl ether of an ethylene glycol having at least two carbon atoms in each alkyl group and not more than two ethylene groups in the glycol portion, and tetrahydrofuran.
Thus the invention is based in part on the discovery that tetrahydrofuran markedly increases the conductivity of Grignard-containing electrolyte, frequently by a factor of 3 to 5 fold.
The inventive ether mixture preferably comprises from about 98 to about 40 percent by weight of a dialkyl ether of an ethylene glycol and from about 2 to about 60 percent by weight of tetrahydrofuran. A more optimum range is from about 90 to about 60% of dialkyl ether of an ethylene glycol and about -40 percent by weight of tetrahydrofuran. It has been found that, under some conditions, too high a tetrahydrofuran concentration may lead to the deposition of solid magnesium halide etherate which may make electrolysis rather diflicult, and accordingly it is desirable but not essential to operate within the foregoing broad range.
The dialkyl ethers of ethylene glycols employed herein are the dialkyl ethers of ethylene glycols having at least two carbon atoms in each alkyl group and not more than two ethylene groups in the glycol portion. Thus the ethers have the formula R-O-(C H O) R, where the R's are the same or different alkyl groups, each having at least twoand suitably up to about 12 carbon atoms per group. n is either one or two. Ethers outside of the foregoing definition tend to form a magnesium chloride etherate which precipitates from the electrolyte, thereby fouling equipment. Examples of Patented Nov. 3, 1964 suitable ethers for use herein include the Carbitols, wherein n is one, and the Cellosolves, wherein n is two. Specific ethers are diethyl Cellosolve, dibutyl Cellosolve, diethyl Carbitol, dibutyl Carbitol, and diethyl hexyl Carbitol.
The alkyl Grignard reagents are chosen to produce the desired tetra-alkyl lead compound. For example, an ethyl Grignard will affordtetraethyl lead while a methyl Grignard will produce tetramethyl lead. The alkyl lead compounds having from 1 to about 4 carbon atoms per alkyl group are most effectively produced by the electrolytic process. By employing mixed Grignard reagents, such as a mixture of ethyl Grignard and methyl Grignard, a mixed tetra-alkyl compound may be prepared; thus dimethyl diethyl lead may be obtained. The halide portion of the alkyl Grignard reagent may be the chloride, the bromide, or, less desirably, the iodide.
It has heretofore been found that the presence of excess alkyl halide in the electrolyte is of major advantage. Alkyl halide concentrations of, say l-50 weight percent of the total electrolyte, react with magnesium metal which will otherwise plate out on the cathode and short the electrodes; it assists in maintaining a high level of electrolyte conductivity; it reduces side reactions; and it appears to provide a current efiiciency well in excess of the theoretical. With respect to the last-mentioned point, this perhaps is due to the formation of a dialkyl lead compound electrolytically, which may then react with alkyl Grignard reagent chemically to form tetralykyl lead, requiring only two faradays per mol. Ordinarily the alkyl halide will correspond with the alkyl Grignard reagent; for exampe, ethyl chloride would normally be used with ethyl magnesium chloride.
Grignard reagents are well known and no discussion of their preparation is necessary.
Conditions in the electrolytic cell advantageously include a temperature within the range of about 20 to about C., preferably 40-70 C., and optimally about 45-60" C. Anode and cathode current densities are each preferably within the range of about 0.2 to about 35 amperes per square foot. Cell pressures may range from atmospheric to high superatmospheric-up to 300 p.s.i.g. or even higher. :Alkyl Grignard concentrations before the onset of electrolysis are advantageously within the range of about 1.5-3.5 Normal, and eletrolysis maybe continued until the electrolyte contains as little as 0.3 Normal Grignard, or even less.
The ability of tetrahydrofuran to increase electrolyte conductivity is quite remarkable, and no present mechanism is available to explain this property. Nonetheless when, for example, a 1.5 N ethyl magnesium chloride solution is made up in dibutyl Carbitol, the specific resitance is 15,000 ohm-centimeters, while an identical solution but containing only 5.4 weight percent tetrahydrofuran has a specific resistance of 9,800 ohm-centimeters. Similarly, a 1.5 Normal ethyl magnesium chloride solution containing 10.8 weight percent tetrahydrofuran has a specific resistance of 6,700 ohm-centimeters, and a' 21.6% tetrahydrofuran solution has a specific resistance of 3,600 ohm-centimeters.
To more fully describe and to exemplify the present invention, the following illustrative embodiments are presented. It will be understood that these are for illustrative purposes only, and accordingly the conditions and quantities are not necessarily definitive with respect to scope or conditions.
Example I furan to produce tetramethyl lead. e To an electrolytic cell having three lead electrodes spaced about one-eighth inch apart and each being a two inch by 3 inch rectangle, 190 grams of a 2.0 Normal methyl magnesium chloride solution in dibutyl Carbitol is added. The outer plates are connected together to serve as a cathode. Cell characteristics are determined by applying progressively increasing voltages across the electrodes and measuring the amperages.
To the electrolyte is added 21.4 grams of tetrahydrofuran. Again cell characteristics are determined, and the results are presented below. Keeping in mind that Grignard normality decreases upon dilution with tetrahydrofuran, the results are even more striking.
Original Solution With Tetrahydrofuran Volts Volts Methyl chloride is added in three portions for a total of 30 grams. Electrolysis is commenced at an initial voltage of volts and at a temperature of 30 C. The run is terminated when, after about 10 ampere hours, cell current falls to 0.02 ampere.
Unreacted methyl chloride is bled 01? and the cell contents are transferred to a flask. Two liquid layers separate out, a clear upper layer containing tetrahydrofuran, dibutyl Carbitol, and tetramethyl lead with only a trace of Grignard (0.01 Normal), and a dark viscous lower layer containing residual Grignard reagent, magnesium chloride etherate, and some tetramethyl lead, tetrahydrofuran, and dibutyl Carbitol. The upper phase contains 19 weight percent tetramethyl lead and represents roughly 50% of the total tetramethyl lead produced.
Both phases are hydrolyzed with ice and aqueous hydrochloric acid. The organic phase is steam distilled at about 100 C. The overhead distillate contains tetrahydrofuran as well as tetramethyl lead, and is repeatedly water Washed to remove the tetrahydrofuran.
Tetramethyl lead is recovered in a yield of 19.1 grams, and remains water white after exposure to light for several weeks.
Example II In this example a methyl Grignard reagent is electrolyzed with an ether mixture containing 40%' tetrahydrofuran and 60% dibutyl Carbitol by weight.
One hundred seventy grams of a 1.8 Normal methyl magnesium chloride solution is placed in an electrolytic cell having 6 square inches of anode surface area and arranged as in the cell of Example I, except that elecslowly as Grignard is converted to tetramethyl lead and magnesium chloride.
After 2 hours of electrolysis, an additional charge of 11 grams of methyl chloride is introduced, and electrolysis is continued fora total of 10.1 ampere hours.
The cell contents are then hydrolyzed with saturated aqueous ammonium chloride solution and the liquid phase which separates out is steam distilled. The overhead mixture of tetramethyl lead and tetrahydrofuran is washed repeatedly with aqueous sodium chloride.
Tetramethyl lead is recovered in a yield of 24.9 grams. By gas chromatography the product is shown to contain more than 95% tetramethyl lead by weight.
Thus while the invention has been described with reference to a particular embodiment thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the appended claims.
We claim:
1. In a process for preparing a tetra-alkyl lead compound by electrolyzing an electrolyte comprising an alkyl Grignard reagent, excess alkyl halide, and an ether, with a lead anode, the improvement characterized by superior electrolyte conductivity which comprises effecting said electrolysis in the presence of an ether mixture comprising, in conjoint presence, from about 98 to about 40% by Weight of a dialkyl ether of an ethylene glycol having at least two carbon atoms in each alkyl group and not more than two ethylene groups in the glycol portion, and from about 2 to about 60% by weight of tetrahydrofuran.
2. Process of claim 1 wherein said tetra-alkyl lead compound is tetraethyl lead.
3. Process of claim 1 wherein said tetra-alkyl lead compound is tetramethyl lead.
4. Process of claim 1 wherein said ether mixture comprises from about to about 60% of said dialkyl ether {of an ethylene glycol and from about 10 to about 40% of tetrahydrofuran.
5. Process of claim 1 wherein said dialkyl ether of an ethylene glycol is dibutyl ether of diethylene glycol.
6. Process of claim 1 wherein said dialkyl ether of an ethylene glycol is ethyl hexyl ether of diethylene glycol.
References Cited in the file of this patent UNITED STATES PATENTS 2,944,948 Giraitis July 12, 1960 2,960,450 Giraitis et al Nov. 15, 1960 3,007,857 Braithwaite Nov. 7, 1961 3,007,858 Braithwaite Nov. 7, 1961 OTHER REFERENCES Kondyrew: Berichte de Deutsche Chemische Gesellschaft, volume 58 (1925), pages 459-463.
Pearson et al.: Transactions Electrochemical Society, volume 82 (1942), pages 297304.

Claims (1)

1. IN A PROCESS FOR PREPARING A TETRA-ALKYL LEAD COMPOUND BY ELECTROLYZING AN ELECTROLYTE COMPRISING AN ALKYL GRIGNARD REAGENT, EXCESS ALKYL HALIDE, AND AN ETHER, WITH A LEAD ANODE, THE IMPROVEMENT CHARACTERIZED BY SUPERIOR ELECTROLYTE CONDUCTIVITY WHICH COMPRISES EFECTING SAID ELECTROLYSIS IN THE PRESENCE OF AN ETHER MIXTURE COMPRISING, IN CONJOINT PRESENCE, FROM ABOUT 98 TO ABOUT 40% BY WEIGHT OF A DIALKYL ETHER OF AN ETHYLENE GLYCOL HAVING AT LEAST TWO CARBON ATOMS IN EACH ALKYL GROUP AND NOT MORE THAN TWO ETHYLENE GROUPS IN THE GLYCOL PORTION, AND FROM ABOUT 2 TO ABOUT 60% BY WEIGHT OF TETRAHYDROFURAN.
US35441A 1960-03-15 1960-06-13 Preparation of organic lead compounds Expired - Lifetime US3155602A (en)

Priority Applications (29)

Application Number Priority Date Filing Date Title
NL262356D NL262356A (en) 1960-03-15
LU39891D LU39891A1 (en) 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 (en) 1960-03-15 1961-03-14 A procedure to make a tetraalcohyll lead product (Machine-translation by Google Translate, not legally binding)
DEST17583A DE1157616B (en) 1960-03-15 1961-03-15 Process for the production of tetraalkyl lead
FR855672A FR1287026A (en) 1960-03-15 1961-03-15 Improvements in processes for the preparation of tetraalkylated lead compounds
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
SE6606793A SE375521B (en) 1960-03-15 1966-05-17
SE7011413A SE379040B (en) 1960-03-15 1966-05-17
IL25803A IL25803A (en) 1960-03-15 1966-05-17 Antimicrobial compositions containing nitrated alkamines and new nitrated alkamines
NO163070A NO115641B (en) 1960-03-15 1966-05-18
GB22126/66A GB1142337A (en) 1960-03-15 1966-05-18 Amino nitroalkanes and their use as microbiocides
BR179699/66A BR6679699D0 (en) 1960-03-15 1966-05-20 PROCESS FOR THE PREPARATION OF AMINO-MITROALKANS AND PESTICIDAL COMPOSITES BASED ON THE SAME
AT1227268A AT314092B (en) 1960-03-15 1966-05-20 Process for the inhibition of the growth of lower animals or plants and means for its implementation
DK258666AA DK125262B (en) 1960-03-15 1966-05-20 Bactericides, fungicides, nematocides and algicides.
DE1620004A DE1620004C3 (en) 1960-03-15 1966-05-20 Pesticides containing N-0-phenyl-2-nitropropyi) -piperacias, their metal salts and such compounds
NL6606997.A NL159975C (en) 1960-03-15 1966-05-20 METHOD FOR PREPARING SECONDARY OR TERTIARY N- (2-NITROALKYL) AMINES ACTIVE AGAINST HARMFUL ORGANISMS; PROCESS FOR PREPARING PREPARATIONS ACTIVE AGAINST HARMFUL ORGANISMS; THE MOLDED PRODUCTS THEREFORE OBTAINED, AND PROCEDURE FOR CONTROLLING MICROORGANISMS THAT CAUSE SLUMMATION AND DEGRADATION IN PAPER MANUFACTURE.
AT481966A AT288340B (en) 1960-03-15 1966-05-20 Process for the preparation of aminonitroalkanes
IT11441/66A IT986753B (en) 1960-03-15 1966-05-20 PROCEDURE FOR THE PRODUCTION OF USEFUL AMINO NITROALKANES SUCH AS INSECTICIDES AND SIMILAR FUNGICIDES AND PRODUCT OBTAINED
FR62411A FR1494137A (en) 1960-03-15 1966-05-20 Antimicrobial and pesticide compounds and compositions, their manufacturing processes and applications in agriculture and industry
BE681371D BE681371A (en) 1960-03-15 1966-05-20
FI661331A FI51171C (en) 1960-03-15 1966-05-20 Aminonitroalkanes for use as antimicrobial agents.
CH119169A CH534121A (en) 1960-03-15 1966-05-23 Process for the preparation of compounds substituted with an amino group on the B-C atom and with a nitro group on the a-C atom
CH119269A CH505551A (en) 1960-03-15 1966-05-23 Pesticides
CH739566A CH490318A (en) 1960-03-15 1966-05-23 Process for the preparation of compounds substituted with an amino group on the B carbon atom and with a nitro group on the a carbon atom

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

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US3155602A true US3155602A (en) 1964-11-03

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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

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US35078A Expired - Lifetime US3118825A (en) 1960-03-15 1960-06-09 Electrochemical process for the production of organometallic compounds

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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)

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US (5) US3118825A (en)
AT (2) AT288340B (en)
BE (1) BE681371A (en)
BR (1) BR6679699D0 (en)
CH (3) CH505551A (en)
DE (2) DE1157616B (en)
DK (1) DK125262B (en)
FI (1) FI51171C (en)
GB (2) GB984421A (en)
IL (1) IL25803A (en)
IT (1) IT986753B (en)
LU (1) LU39891A1 (en)
NL (2) NL159975C (en)
NO (1) NO115641B (en)
SE (2) SE375521B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3256161A (en) * 1961-02-13 1966-06-14 Nalco Chemical Co Manufacture of tetramethyl lead
US3312605A (en) * 1961-02-13 1967-04-04 Nalco Chemical Co Preparation of organo metallic compounds
US3359291A (en) * 1964-10-05 1967-12-19 Nalco Chemical Co Purification of tetraalkyl lead
US3431185A (en) * 1964-05-11 1969-03-04 Ethyl Corp Hydrocarbon lead production
US3522156A (en) * 1964-10-21 1970-07-28 Ethyl Corp Production of hydrocarbon lead compounds

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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
BE671841A (en) * 1964-11-05
US3403983A (en) * 1965-01-11 1968-10-01 Mallinckrodt Chemical Works Steam distillation of metal values in solution
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
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
JPH03502929A (en) * 1988-09-06 1991-07-04 ザ　ルブリゾル　コーポレーション Nitro group-containing amine and fuel composition containing the same
US9145341B2 (en) * 2012-11-19 2015-09-29 Technion Research & Development Foundation Limited Process of preparing Grignard reagent

Citations (4)

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US2944948A (en) * 1956-02-06 1960-07-12 Ethyl Corp Method of purifying organometallic complexes and their use in the preparation of organolead compounds
US2960450A (en) * 1959-10-16 1960-11-15 Ethyl Corp Organo manganese compounds
US3007858A (en) * 1959-05-06 1961-11-07 Nalco Chemical Co Preparation of organo metallic compounds
US3007857A (en) * 1957-07-31 1961-11-07 Nalco Chemical Co Preparation of organic lead compounds

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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
NL101542C (en) * 1954-11-26
US3028319A (en) * 1960-02-01 1962-04-03 Ethyl Corp Manufacture of magnesium organo compounds

Patent Citations (4)

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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
US3007857A (en) * 1957-07-31 1961-11-07 Nalco Chemical Co Preparation of organic lead compounds
US3007858A (en) * 1959-05-06 1961-11-07 Nalco Chemical Co Preparation of organo metallic compounds
US2960450A (en) * 1959-10-16 1960-11-15 Ethyl Corp Organo manganese compounds

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3256161A (en) * 1961-02-13 1966-06-14 Nalco Chemical Co Manufacture of tetramethyl lead
US3312605A (en) * 1961-02-13 1967-04-04 Nalco Chemical Co Preparation of organo metallic compounds
US3431185A (en) * 1964-05-11 1969-03-04 Ethyl Corp Hydrocarbon lead production
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

Also Published As

Publication number Publication date
FI51171B (en) 1976-08-02
GB1142337A (en) 1969-02-05
US3584050A (en) 1971-06-08
CH534121A (en) 1973-02-28
DE1620004A1 (en) 1970-02-12
NL159975C (en) 1979-09-17
NO115641B (en) 1968-11-04
CH490318A (en) 1970-05-15
NL159975B (en) 1979-04-17
DK125262B (en) 1973-01-29
FI51171C (en) 1976-11-10
NL262356A (en)
BE681371A (en) 1966-11-21
NL6606997A (en) 1966-11-22
AT288340B (en) 1971-02-25
BR6679699D0 (en) 1973-04-12
CH505551A (en) 1971-04-15
US3164537A (en) 1965-01-05
GB984421A (en) 1965-02-24
US3118825A (en) 1964-01-21
DE1620004B2 (en) 1978-09-14
DE1620004C3 (en) 1979-05-10
SE379040B (en) 1975-09-22
IT986753B (en) 1975-01-30
DE1157616B (en) 1963-11-21
IL25803A (en) 1971-05-26
AT314092B (en) 1974-03-25
SE375521B (en) 1975-04-21
LU39891A1 (en)
US3298939A (en) 1967-01-17

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