US2635106A - Process for making tetraethyl lead - Google Patents

Process for making tetraethyl lead Download PDF

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Publication number
US2635106A
US2635106A US253131A US25313151A US2635106A US 2635106 A US2635106 A US 2635106A US 253131 A US253131 A US 253131A US 25313151 A US25313151 A US 25313151A US 2635106 A US2635106 A US 2635106A
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United States
Prior art keywords
alloy
per cent
yield
tetraethyllead
lead
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Expired - Lifetime
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US253131A
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English (en)
Inventor
Shapiro Hymin
Witt Earl G De
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Ethyl Corp
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Ethyl Corp
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Priority to NLAANVRAGE7401937,B priority Critical patent/NL171641B/xx
Priority to NL81236D priority patent/NL81236C/xx
Application filed by Ethyl Corp filed Critical Ethyl Corp
Priority to US253131A priority patent/US2635106A/en
Priority to GB9067/52A priority patent/GB716063A/en
Priority to DEE5371A priority patent/DE937350C/de
Priority to FR1062517D priority patent/FR1062517A/fr
Application granted granted Critical
Publication of US2635106A publication Critical patent/US2635106A/en
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    • 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

Definitions

  • NaPb modifies its homogenous crystal lattice, and that on alkylation at normal operating temperatures of around 80 C. the resulting yield of tetraethyllead based on the total reducing metal content is actually lower than that obtained.
  • the sodium-lead alloy alone For example the best yield obtained when about one per cent of magnesium, calcium or sodium itself were added to the sodium-lead alloy, NaPb, was 64, 69, and 84 per cent respectively, underconditions where the yield from NaPb was 88 per cent. However, the yield from NaPb plus one per cent potassium under the same conditions was 92 per cent.
  • curves A and B are respectively catalyzed and non-catalyzed tests using the present commercial alloy, which consists of one atom of sodium to one atom of lead. It should be noted that in commercial practice curves A and B show that little difference in tetraethyllead yield is obtained at 60 0., and higher, between a catalyzed and a non-catalyzed reaction. On the other hand, at temperatures below 60 C. the non-catalyzed yield is higher than the catalyzed yield.
  • Curves C and D represent the data we obtained when operating with an alloy, containing 1.5 weight per cent potassium, in which the atom ratio of total alkali metal to lead is 1 to 1, curve C being the results obtained on a catalyzed reaction and curve D the results obtained on a non-catalyzed reaction. It is to be specifically noted that, not only is the catalyzed yield higher than the non-catalyzed throughout the temperature range as contrasted with curves B and A for the standard sodium-lead alloy, but at temperatures below 40 C. and above 60 C. the improvement between the catalytic and noncatalytic yield is remarkable, entirely unexpected, and could not be predicted.
  • the yield of tetraethyllead falls off considerably if the con tent of sodium varies from 50 atom per cent.
  • the composition of the alloy is quite critical. Thisis not true to such a large extent when the amount of potassium taught. herein is used.
  • the yield of tetraethyllead is always substantially I above 90 per cent. and good yields are obtained outside of this range.
  • the potassium content of three different alloys was kept. constant at one weight per cent but the total alkali metal content was 49, 50 and 52 atom per cent, all.
  • the tetraethyllead yield was 93, Stand 91 per cent respectively, whereas when thesame tests were repeated with an alloy containing-no potassium the yield was always less than 90 per cent and at 53 atom per cent the yield dropped to 84 percent. Likewisev when the above three alloys containing potassium were employed at a 100 reaction temperature the yields were 94, 95 and 93 per cent respectively. However, it should be noted that the highest yields. are obtained when the atomic ratio of alkali metal to lead-is near 1 to 1. Also the sodium content should be between and 35; Weight per cent. s i
  • the temperature range employed should be between 0 and 100? C. and preferably above 60 C.
  • catalyzed and non-catalyzed tetraethyllead yields for dif- Table I Percent Tetraethyllead Based on Alkali Metal in the Alley Charged Temperature Catalyst (Acetone) No Catalyst NaPb NaPb+l.5'7 Alloy K. o
  • reaction time can be varied within 4; toil,- hours and high yields obtained.
  • reaction times /3 hour, 1 hour, 3 hours and 6 hours were used, tetraethyllead yields of 95, 97, 96 and 93 respectively were obtained.
  • The'amount of ethylating agent is not critical as long as it is used in an amount in excess over the.- stoichiometric requirement. Amounts between 1.0 5 and, 30 theories can be successfully employed although we prefer to use an amount between. 1.2 and 10 theories. Likewise the pressure is not critical but must be sufficient to maintain the ethylating agent in the liquid phase.
  • a catalyst is essential to our invention.
  • the acetone catalyst of Example I was left out, theyield of tetraethyllead was only 37 per cent and the non-. catalytic yield never reaches the yield obtainable with a catalyst.
  • the non-catalytic yield may be improved at long reaction times, say 24 hours, unless excessive byproduct. formation prevents it, but such reaction times are impractical and would not be used commercially.
  • Catalysts other than acetone can be successfully employed in our invention.
  • any of the compounds described asrate accelerators in Patents 2,426,598, 2,464,397, 2,464,298, 2,464,399 and 2,477,465 can be used.
  • Othercompounds, diiferent from these in type can also be used, for example, alcohols, ethers, aldehydes, amines, nitriles and peroxides, most of which are not even rate accelerators for the standard NaPb alloy and none improve the yield on such alloy to any extent, although all of them improve the yield on our potassium alloy.
  • Our catalysts are organic compounds soluble. in ethyl chloride, containing a CO, a CN or a CS bond, having a boiling point range between -25 C. and 300 0., having a molecular weight between 30 and 250, having a density of less than 1.6, and having a hydrocarbon radical selected from the class of aliphatics and aromatics; in which the number of carbon atoms is less than 15.
  • ketones including acetone, chloroacetone, acetophenone, benzophenone, cy-' clohexanone, diethylketone, methylethylketone, methylisopropylketone, dibutylketone, and phen--.
  • esters including ethyl acetate, ethyl formate, vinyl acetate, diethyl carbonate, ethyl propionate, methyl acetate, dibutyl carbonate,, ethyl acrylate, ethyl crotonate, benzyl acetate and ethyl benzcate;'alcohols including ethyl loco monsoon W alcohol, methyl alcohol, capryl alcohol, benzyl alcohol, isopropyl alcohol, isobutyl alcohol, butyl alcohol, amyl alcohol, phenylethyl alcohol, and phenylpropyl alcohol; ethers such as allyl ether, propylene oxide, phenylethylene oxide, and 1,2- dimethoxyethane; aldehydes including isobutyraldehyde, benzaldehyde, furfuraldehyde, propionaldehyde, acetalde
  • Aluminum Chloride I The amount of catalyst employed generally diethoxymethane, 1,1-ditemperature and the ratio of reactants, although substantial yields are obtained when the concentration of catalyst varies from the optimum within the above limits.
  • our alloy can be prepared by any of the means found useful for preparing our present alloy.
  • other methods can be employed as follows:
  • a process for making tetraethyllead comprising reacting ethyl chloride with a ternary alloy of sodium, potassium and lead, in which the sodium content is between 5 and 35 weight per cent and the potassium content is between 0.1 and 5 weight per cent, in the presence of an organic lead alkylating catalyst selected from the group consisting of organic oxygen-containing and nitrogen-containing materials, at a temperature below about C., under a pressure such that at the temperature used the ethyl chloride is maintained in the liquid phase, and for a time less than about 8 hours.
  • an organic lead alkylating catalyst selected from the group consisting of organic oxygen-containing and nitrogen-containing materials
  • a process for making tetraethyllead comprising reacting ethyl chloride with a ternary alloy of sodium, potassium and lead in which the potassium content is between 1 and 2 weight per cent, the total sodium and potassium content is between 48 and 52 atom per cent in the presence of an acetone catalyst, at a temperature between 60 and 100 0., under a pressure such that at the temperature used the ethyl chloride is maintained in the liquid phase, and for a time between A and 8 hours.
  • a process for making tetraethyllead comprising reacting ethyl chloride with a ternary alloy of sodium, potassium and lead in which the sodium content is between 5 and 35 weight per cent and the potassium content is between 0.1 and 5 weight per cent, under a pressure such that at the temperature used the ethyl chloride is maintained in the liquid phase, and for a time less than 8 hours, and in the presence of a lead alkylating catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
US253131A 1951-10-25 1951-10-25 Process for making tetraethyl lead Expired - Lifetime US2635106A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
NLAANVRAGE7401937,B NL171641B (nl) 1951-10-25 Inrichting voor het uitlezen van een registratiedrager waarop informatie is aangebracht in een optisch uitleesbare structuur.
NL81236D NL81236C (en:Method) 1951-10-25
US253131A US2635106A (en) 1951-10-25 1951-10-25 Process for making tetraethyl lead
GB9067/52A GB716063A (en) 1951-10-25 1952-04-09 Improvements in or relating to process for making tetraethyllead
DEE5371A DE937350C (de) 1951-10-25 1952-04-23 Verfahren zur Herstellung von Bleitetraaethyl
FR1062517D FR1062517A (fr) 1951-10-25 1952-04-23 Perfectionnements aux procédés de fabrication du plomb tétraéthyle

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US253131A US2635106A (en) 1951-10-25 1951-10-25 Process for making tetraethyl lead

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US2635106A true US2635106A (en) 1953-04-14

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US253131A Expired - Lifetime US2635106A (en) 1951-10-25 1951-10-25 Process for making tetraethyl lead

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US (1) US2635106A (en:Method)
DE (1) DE937350C (en:Method)
FR (1) FR1062517A (en:Method)
GB (1) GB716063A (en:Method)
NL (2) NL171641B (en:Method)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3004998A (en) * 1959-12-08 1961-10-17 Ethyl Corp Stable lead alkyl compositions and a method for preparing the same
US3239548A (en) * 1963-01-11 1966-03-08 Du Pont Process for making tetraethyl lead
US3400143A (en) * 1965-05-17 1968-09-03 Du Pont Process for making tetramethyl lead
US3401188A (en) * 1965-08-05 1968-09-10 Du Pont Process for making tetramethyl lead
US3401187A (en) * 1965-06-15 1968-09-10 Du Pont Process for making tetramethyl lead
US3408375A (en) * 1965-05-17 1968-10-29 Du Pont Process for making tetramethyl lead
US3412123A (en) * 1966-04-27 1968-11-19 Du Pont Substituted cyanamide-accelerated tetraethyl lead process

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1664021A (en) * 1926-11-03 1928-03-27 Du Pont Process of manufacturing tetra-ethyl lead
US1717961A (en) * 1925-10-17 1929-06-18 Du Pont Process for the production of lead tetra-alkyl
US1749567A (en) * 1927-10-15 1930-03-04 Du Pont Alkylated lead
US1962173A (en) * 1928-08-17 1934-06-12 Du Pont Manufacture of tetraethyl lead
US2464397A (en) * 1945-07-04 1949-03-15 Du Pont Manufacturing tetraethyl lead
US2464399A (en) * 1946-04-10 1949-03-15 Du Pont Manufacturing tetraethyl lead

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1717961A (en) * 1925-10-17 1929-06-18 Du Pont Process for the production of lead tetra-alkyl
US1664021A (en) * 1926-11-03 1928-03-27 Du Pont Process of manufacturing tetra-ethyl lead
US1749567A (en) * 1927-10-15 1930-03-04 Du Pont Alkylated lead
US1962173A (en) * 1928-08-17 1934-06-12 Du Pont Manufacture of tetraethyl lead
US2464397A (en) * 1945-07-04 1949-03-15 Du Pont Manufacturing tetraethyl lead
US2464399A (en) * 1946-04-10 1949-03-15 Du Pont Manufacturing tetraethyl lead

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3004998A (en) * 1959-12-08 1961-10-17 Ethyl Corp Stable lead alkyl compositions and a method for preparing the same
US3239548A (en) * 1963-01-11 1966-03-08 Du Pont Process for making tetraethyl lead
US3400143A (en) * 1965-05-17 1968-09-03 Du Pont Process for making tetramethyl lead
US3408375A (en) * 1965-05-17 1968-10-29 Du Pont Process for making tetramethyl lead
US3401187A (en) * 1965-06-15 1968-09-10 Du Pont Process for making tetramethyl lead
US3401188A (en) * 1965-08-05 1968-09-10 Du Pont Process for making tetramethyl lead
US3412123A (en) * 1966-04-27 1968-11-19 Du Pont Substituted cyanamide-accelerated tetraethyl lead process

Also Published As

Publication number Publication date
NL81236C (en:Method)
NL171641B (nl)
FR1062517A (fr) 1954-04-23
DE937350C (de) 1956-01-05
GB716063A (en) 1954-09-29

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