US3118825A - Electrochemical process for the production of organometallic compounds - Google Patents

Electrochemical process for the production of organometallic compounds Download PDF

Info

Publication number
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
Authority
US
United States
Prior art keywords
alkyl
tetra
lead
ether
lead compound
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
Application number
US35078A
Other languages
English (en)
Inventor
Linsk Jack
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Standard Oil Co
Original Assignee
Standard Oil Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to LU39891D priority Critical patent/LU39891A1/xx
Priority to NL262356D priority patent/NL262356A/xx
Application filed by Standard Oil Co filed Critical Standard Oil Co
Priority to US35078A priority patent/US3118825A/en
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/es
Priority to FR855672A priority patent/FR1287026A/fr
Priority to DEST17583A priority patent/DE1157616B/de
Priority to GB9445/61A priority patent/GB984421A/en
Publication of US3118825A publication Critical patent/US3118825A/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 IL25803A priority patent/IL25803A/xx
Priority to SE7011413A priority patent/SE379040B/xx
Priority to NO163070A priority patent/NO115641B/no
Priority to GB22126/66A priority patent/GB1142337A/en
Priority to DK258666AA priority patent/DK125262B/da
Priority to FR62411A priority patent/FR1494137A/fr
Priority to NL6606997.A priority patent/NL159975C/xx
Priority to BR179699/66A priority patent/BR6679699D0/pt
Priority to AT481966A priority patent/AT288340B/de
Priority to IT11441/66A priority patent/IT986753B/it
Priority to DE1620004A priority patent/DE1620004C3/de
Priority to AT1227268A priority patent/AT314092B/de
Priority to BE681371D priority patent/BE681371A/xx
Priority to FI661331A priority patent/FI51171C/fi
Priority to CH739566A priority patent/CH490318A/de
Priority to CH119169A priority patent/CH534121A/de
Priority to CH119269A priority patent/CH505551A/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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.

Landscapes

  • 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)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Hydrogenated Pyridines (AREA)
  • Plural Heterocyclic Compounds (AREA)
US35078A 1960-03-15 1960-06-09 Electrochemical process for the production of organometallic compounds Expired - Lifetime US3118825A (en)

Priority Applications (29)

Application Number Priority Date Filing Date Title
LU39891D LU39891A1 (US07122603-20061017-C00045.png) 1960-03-15
NL262356D NL262356A (US07122603-20061017-C00045.png) 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
FR855672A FR1287026A (fr) 1960-03-15 1961-03-15 Perfectionnements apportés aux procédés pour la préparation de composés tétraalcoylés du plomb
DEST17583A DE1157616B (de) 1960-03-15 1961-03-15 Verfahren zur Herstellung von Tetraalkylblei
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 (US07122603-20061017-C00045.png) 1960-03-15 1966-05-17
IL25803A IL25803A (en) 1960-03-15 1966-05-17 Antimicrobial compositions containing nitrated alkamines and new nitrated alkamines
SE7011413A SE379040B (US07122603-20061017-C00045.png) 1960-03-15 1966-05-17
NO163070A NO115641B (US07122603-20061017-C00045.png) 1960-03-15 1966-05-18
GB22126/66A GB1142337A (en) 1960-03-15 1966-05-18 Amino nitroalkanes and their use as microbiocides
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
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
FI661331A FI51171C (fi) 1960-03-15 1966-05-20 Mikrobinvastaisina aineina käytettävät aminonitroalkaalit.
DE1620004A DE1620004C3 (de) 1960-03-15 1966-05-20 N-0-Phenyl-2-nitropropyi)-Piperazien, dessen Metallsalze und solche Verbindungen enthaltendes Schädlingsbekämpfungsmittel
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.
BR179699/66A BR6679699D0 (pt) 1960-03-15 1966-05-20 Processo para a preparacao de amino-mitroalcanos e composicoes pesticidas a base dos mesmos
AT481966A AT288340B (de) 1960-03-15 1966-05-20 Verfahren zur Herstellung von Aminonitroalkanen
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
BE681371D BE681371A (US07122603-20061017-C00045.png) 1960-03-15 1966-05-20
DK258666AA DK125262B (da) 1960-03-15 1966-05-20 Baktericid, fungicid, nematocid og algicid.
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
CH119269A CH505551A (de) 1960-03-15 1966-05-23 Schädlingsbekämpfungsmittel
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

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 (US07122603-20061017-C00045.png)
AT (2) AT314092B (US07122603-20061017-C00045.png)
BE (1) BE681371A (US07122603-20061017-C00045.png)
BR (1) BR6679699D0 (US07122603-20061017-C00045.png)
CH (3) CH534121A (US07122603-20061017-C00045.png)
DE (2) DE1157616B (US07122603-20061017-C00045.png)
DK (1) DK125262B (US07122603-20061017-C00045.png)
FI (1) FI51171C (US07122603-20061017-C00045.png)
GB (2) GB984421A (US07122603-20061017-C00045.png)
IL (1) IL25803A (US07122603-20061017-C00045.png)
IT (1) IT986753B (US07122603-20061017-C00045.png)
LU (1) LU39891A1 (US07122603-20061017-C00045.png)
NL (2) NL159975C (US07122603-20061017-C00045.png)
NO (1) NO115641B (US07122603-20061017-C00045.png)
SE (2) SE379040B (US07122603-20061017-C00045.png)

Cited By (6)

* 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
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)

* Cited by examiner, † Cited by third party
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 (US07122603-20061017-C00045.png) * 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
JPH03502929A (ja) * 1988-09-06 1991-07-04 ザ　ルブリゾル　コーポレーション ニトロ基含有アミンおよびそれを含有する燃料組成物

Citations (2)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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 (US07122603-20061017-C00045.png) * 1954-11-26
BE569921A (US07122603-20061017-C00045.png) * 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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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)

* 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
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
IL25803A (en) 1971-05-26
SE375521B (US07122603-20061017-C00045.png) 1975-04-21
DK125262B (da) 1973-01-29
CH505551A (de) 1971-04-15
AT288340B (de) 1971-02-25
CH490318A (de) 1970-05-15
US3584050A (en) 1971-06-08
US3164537A (en) 1965-01-05
NL159975B (nl) 1979-04-17
GB1142337A (en) 1969-02-05
BR6679699D0 (pt) 1973-04-12
NL6606997A (US07122603-20061017-C00045.png) 1966-11-22
NO115641B (US07122603-20061017-C00045.png) 1968-11-04
US3155602A (en) 1964-11-03
BE681371A (US07122603-20061017-C00045.png) 1966-11-21
DE1620004A1 (de) 1970-02-12
US3298939A (en) 1967-01-17
CH534121A (de) 1973-02-28
FI51171C (fi) 1976-11-10
IT986753B (it) 1975-01-30
DE1620004C3 (de) 1979-05-10
AT314092B (de) 1974-03-25
GB984421A (en) 1965-02-24
FI51171B (US07122603-20061017-C00045.png) 1976-08-02
DE1157616B (de) 1963-11-21
LU39891A1 (US07122603-20061017-C00045.png)
DE1620004B2 (de) 1978-09-14
NL262356A (US07122603-20061017-C00045.png)
NL159975C (nl) 1979-09-17
SE379040B (US07122603-20061017-C00045.png) 1975-09-22

Similar Documents

Publication Publication Date Title
US3118825A (en) Electrochemical process for the production of organometallic compounds
Cope et al. Molecular asymmetry. IX. Partial resolution and asymmetric synthesis of 1, 2-cyclononadiene
US4035242A (en) Distillative purification of alkane sulfonic acids
US3024170A (en) Process of azeotropic distillation of formic acid from acetic acid
KR19980702932A (ko) 메탄올로부터 디메틸 에테르를 제조하고 회수하는 방법
US2140694A (en) Dehydration of organic oxy compounds
US2762760A (en) Extractive distillation of phenol-containing mixtures
US3649482A (en) Cathodic process for the preparation of tetraalkyl lead compounds
US4092257A (en) Constant boiling admixtures of toluene/perfluoro-n-heptane
US4666563A (en) Separation of isopropyl ether from isopropanol and water by extractive distillation
US2591712A (en) Extractive distillation of closeboiling organic compounds from their liquid mixtures
US4153809A (en) Extractive separation of glycolic acid from diglycolic acid
US4551208A (en) Recovery of formic acid by distillation
JPH11511452A (ja) 二圧蒸留によるブタノール及びジブチルエーテルの分離
JP2602696B2 (ja) 黒酸からのアクリル酸およびまたはアクリル酸エチルの回収方法
Bank et al. Reactions of aromatic radical anions. X. Syntheses using a conveniently recoverable radical anion precursor
US2684934A (en) Process for drying methyl ethyl ketone
CA1093537A (en) Oximes and process for the separation of copper values from aqueous solutions
US2413245A (en) Azeotropic distillation of toluene
US2667502A (en) Purifying synthetic water-soluble carboxylic acids
US3151139A (en) Countercurrent extraction and purification of secondary and tertiary saturated unsubstituted c9-c19 monocarboxylic acids
US2228027A (en) Process for the catalytic conversion of olefins to alcohols
Drabowicz et al. A NEW ASYMMETRIC SYNTHESIS OF CHIRAL t-BUTYL t-BUTANETHIOSULPHINATE1
US3839458A (en) Separation of acetaldehyde from 3-hydroxybutanal using a cycloalkane
US3380899A (en) Electrolytic preparation and recovery of tetraalkyl lead compounds