US2535193A - Process for making hydrocarbonlead compounds - Google Patents

Process for making hydrocarbonlead compounds Download PDF

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Publication number
US2535193A
US2535193A US135021A US13502149A US2535193A US 2535193 A US2535193 A US 2535193A US 135021 A US135021 A US 135021A US 13502149 A US13502149 A US 13502149A US 2535193 A US2535193 A US 2535193A
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Prior art keywords
lead
parts
chloride
reaction
halide
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US135021A
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English (en)
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Calingaert George
Shapiro Hymin
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Ethyl Corp
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Ethyl Corp
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Priority to US135021A priority Critical patent/US2535193A/en
Priority to GB9343/50A priority patent/GB673440A/en
Priority to FR1018934D priority patent/FR1018934A/fr
Priority to DEE1168A priority patent/DE848817C/de
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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

  • This invention relates to a process for the manufacture of hydrocarbon-lead compounds, particularly alkyllead compounds. More specifically our invention is directed to an improved process for the manufacture of tetraethyllead.
  • the process employed in present commercial practice for the manufacture of tetraethyllead has been in use for a number of years and, in general, is satisfactory. However, it has certain disadvantages which are overcome by practicing our invention.
  • the present commercial process proceeds by reacting a sodium-lead alloy of composition controlled to correspond substantially to NaPb with ethyl chloride according to the equation:
  • the free lead produced in the (irisnard reaction will not react with additional quantitles of C2I'I5MQC1 and thus it must be recovered, purified, and ii reused, converted to lead chloride. This is tedious, expensive and inefficient. In part, it accounts for the fact that, so far as we are aware, the Grignard reaction has never been applied to any extent commercially to the production of tetraethyllead or any other organic lead compounds. Despite its drawbacks, therefore, the present commercial operation is a more efiicient and desirable process than any based upon the Grignard reaction, due in part to the high cost of lead chloride and the expense involved in reconverting the free lead to lead chloride.
  • hydrocarbon-lead compounds can be made by reacting free lead with an alkylating or arylating agent and a compound correspondin to the general formula RMgX, in which R is a hydrocarbon radical and X is a halide.
  • RMgX a hydrocarbon radical
  • X a halide
  • R may be ethyl and X may be chlorine.
  • the lead used in the process of our invention is any form of metallic lead. which from its physical state, degree of comminution, and conditions of surface is reactive with an alkvlating or arylatin agent and an alkvlor arylmagnesium halide to produce an alk lor aryllead.
  • the lead should be finely divided and its surface s ould be free from oxidation, which would decrease its activity. It is to be noted that substantial yields of tetraethyllead have been obtained in our rocess from an oxidized form of lead. Ho ever. the removal of, or the prevention of the formation of oxidized material on the lead urface materially increases the yield obtainable.
  • the unreacted lead remaining from kno n processes in which some alkyllead is formed is an especially excellent form of lead for use in our invention.
  • the unreacted lead remaining from the present commercial process when treated according to our inv ntion with ethyl chloride. and ethylmagnesium ch oride. results in a yield of about '79 per cent of alkyllead based on the unreact d lead c ar ed.
  • the lead efliciency i. e.
  • lead powders resulting from the decomposition of organo-lead compounds by heat such as for instance, the lead deposited during the thermal decomposition of organo-lead compounds.
  • Certain other forms of lead powders which are sunlciently active for use in making tetraethyllead by our process can be prepared by grinding or otherwise comminuting lead metal or massive lead especially when this is done in an atmos phere of nitrogen or under an appropriate liquid, which prevents the oxidation of the lead surface.
  • a further example of a method of preparing a finely divided lead suitable for practicing our invention is the reductive precipitation of lead from its compounds. Other methods such as electrolytic deposition will occur. to those skilled in the art.
  • Lead alloys particularly allows containing alkaline earth and alkali metals, are also a good source oflead and have been successfully employed.
  • Sodium-lead alloy is an especially good alloy for such use.
  • Other examples of metals alloyed with the lead which can be successfully used in practicing our invention are calcium,
  • Metal-lead alloy-l-ethyl chloride tetraethyllead+lead+metal chloride
  • Our invention is adaptable to the production of alkyllead, aryllead or mixed alkylaryllead compounds generally, such as tetraethyllead, tetramethyllead, dimethyldiethyllead, triethylphenyllead, tetrapropyllead, and tetraphenyllead.
  • alkyllead, aryllead or mixed alkylaryllead compounds generally, such as tetraethyllead, tetramethyllead, dimethyldiethyllead, triethylphenyllead, tetrapropyllead, and tetraphenyllead.
  • tetraethyllead the most widely known because of its
  • the process of our invention is conducted as follows: lead. for example in the form of sodium-lead alloy, NaPb, is first placed in a reaction vessel such as the autoclave of the present commercial process.
  • the alkylmagnesium halide may also be added at this time although it is preferable to add it after the reaction vessel is closed.
  • the vessel is then closed exce t for the liquid feed line through which the fluid reactants are passed and a line to a reflux condenser.
  • the necessary quantity of alkylat-- ing agent such as ethyl chloride is then introduced into the autoclave followed by delivery of the alkylmacnesium halide such as ethylmagnesium chloride, or the latter can be added along with the ethyl chloride.
  • the ethylmagnesium chloride is added after the customary reaction between the alloy and the alkylating agent is initiated.
  • the alkylmagnesium chloride is not added until most of the customary reaction between the alloy and the'alkylating agent has occurred.
  • the preferred methods of operating our process using a lead alloy such as sodium-lead alloy are the method of reaction wherein the alkylmagnesium halide is added prior to or concurrently with the alkylating agent, hereinafter referred to as the one-stage process, and the method wherein most of the alkylmagnesium halide along with additional quantities of alkylating agent is added after the customary reaction is substantially completed, hereafter referred to as the two-stage process.
  • the two-stage process variations in the above modifications can be made such as introducing part of the alkylmagnesium halide along with the initial feed of the alkylating agent followed by additional alkylmagnesium halide after most of the customary reaction has occurred.
  • ether refers to diethyl ether unless otherwise specified.
  • EXAMPLE I Two-stage reaction using sodium-lead alloy and ethyl chloride
  • a charge of 100 parts of NaPb alloy was added to a reaction vessel equipped with an agitator, a jacket for circulation of heating or cooling liquids, a reflux condenser, charging and discharging ports, liquid feed'lines, and means for releasing the pressure.
  • Liquid ethyl chloride in the amount of 167 parts was added under pressure to the stirred solids in the vessel over a period of one-half hour.
  • the temperature of the reaction mass was permitted to rise from an initial temperature of 50 C. to a temperature of 70 C. during this feed period.
  • the autoclave was maintained at a temperature of C. and a pressure of approximately 130 pounds per square inch gauge for an additional minutes. At the end of this period the pressure in the autoclave was reduced to atmospheric by venting for 1-5 minutes while the temperature was maintained at 70 C. For an additional period of 15 minutes at 70 C. nitrogen was passed over the reaction mass with the autoclave open to the atmosphere. The mass was then cooled to 45 C. over an additional 30 minute period while flushing with a stream of nitrogen. The reaction mass was then discharged to a steam-still containing 250 parts of water. With C. steam fed to the jacket of the steamstill, a forecut of ethyl chloride and ether was taken, up to a vapor temperature of 70 C. At'
  • EXAMPLE II One-stage reaction using sodium-lead alloy and ethyl chloride
  • a one-stage modification was carried out with the variation that the other solution of ethylmagnesium chloride was added simultaneously with the charge of ethyl chloride to the alkyllead autoclave containing the sodium-lead alloy over a perind of 415 minutes.
  • 100 parts of sodium-lead alloy 167 parts of ethyl chloride, 57.4 of ethylmagnesium chloride and 95.9 parts of ether were employed.
  • the operations of cooking, venting, cooling, discharging and recovery of the product were conducted substantially as above.
  • the yield of product was 66.7 parts, or 47.5 per cent based on the lead present 5 in the sodium-lead alloy.
  • Example III The process of Example I was carried out until the reaction between the ethyl chloride and the sodiumdead alloy was substantially complete, that is after the cooking period of 15 minutes at a temperature of 76 C. was completed.
  • the autoclave was then vented to atmospheric pressure over a period of 15 minutes with the agitator in a. motion and the temperature maintained at 70 (3., thereby removing substantially all the unreaoted ethyl chloride.
  • a solution of 57.4 parts of ethylmagnesiurn chloride in 95.8 parts of ether and containing an additional 167 parts of ethyl chloride was then added to the autoclave during a period of 45 minutes.
  • the operations of cooking, venting, cooling, discharging and recovery of the product were conducted substantially as in Example I above.
  • the yield of product was 117 parts, or 83.5 per cent based on the lead present in the sodium-lead alloy.
  • EXAMPLE IV In place of the sodium-lead alloy of the fore- '"I going examples 168 parts of a lead powder were added to the autoclave and 250 parts of ethyl chloride, and 85.7 p rts of ethyl magnesium chloride in 143 parts of ether were added in the sequence and under the conditions of Example II. The additional operations of cooking, venting,
  • Example II The yield of product was 109 parts, or 77.8 per cent based on the lead metal charged.
  • alkylating and arylating agents can be employed in our invention.
  • the alkylating and arylating agents of our process are organic compounds which may be represented by RX, having the desired alkyl or aryl group, R, attached to a negative atom or radical, X, capable of reacting with the magnesium of the hydrocarbon-magnesium halide to form the corresponding magnesium salts, MgXz, as shown in the above equation for a typical embodiment of the process of our invention.
  • these alkylating and arylating agents are esters of inorganic acids such as the alkyl and aryl chlorides, bromides, iodides and phosphates.
  • the inorganic acid ester alkylating and arylating agents are the monochloro, -bromo and -iodo derivatives of the parafiin and aromatic hydrocarbons such as methane, ethane, propane, butane, pentane, and benzene and the corresponding trialkyl phosphates.
  • methyl chloride, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, n-propyl chloride, n-butyl chloride, n-butyl bromide, n-amyl chloride, n-amyl iodide, phenyl bromide and triethyl phosphate can be successfully employed.
  • other isomers such as the iso compounds can be used.
  • Various combinations of these alkylating agents can also be used.
  • two or more alkylating or arylating agents can be used simultaneously in the oneand two-stage process or different alkylating or arylating agents .can be used in each stage of the two-stage process.
  • the alkylating agents which are well known for use in the present commercial process, or hich can he used in our rocess with a lead alloy, ive xcellent results wh n em loyed in all em od ments of our invention.
  • Those alkvlating or arylating ag nts which give relatively low yields in the present commercial process, or in our process in which a lead alloy is em loyed, do, however, give excellent results when free lead orthe lead resulting from the roces es ofthe prior art are em loyed, or are em loyed in the second stage of the two-stage embodiment of our invention. re ard es of the form in which the lead is em loy d in the first stage.
  • the alkvlating and arylating agents of our process sho ld be employed in excess over the amount required according to the equation for our reaction as given previously herein'. If less than the amount of alkvlatingagent reouired to completely alkyl te the lead according to the above equation of a typical example of our pro e s is used. the yields will be lower, but will still be good when determined on the ba is of the amount of alkylating agent. This is especially true when the two-stage operation is employed and in an operation wherein the alkylat ing agent is fed to the system gradually in a batch or continuous operation.
  • the hydrocarbon-magnesium halide of our process illustrated by the RMgX in the above typical equation of our process, consists of the desired alkyl or aryl radical, R, and a halide, X, selected from chlorine, bromine or iodine.
  • hydrocarbon-magnesium halides prepared by reacting normal alkyl halides with metallic magnesium
  • other isomers can be employed such as those derived from the iso and secondary alkyl halides.
  • Various combinations of hydrocarbon-magnesium halides can also be used.
  • any of the usual solvents or cata ysts normally employed in the preparation of hydrocarbonmagnesium halides can be successfully employed in preparing hydrocarbon-magnesium halides for use in the process of our invention.
  • solvents which can be employed include the ali hatic ethers such as diethyl ether, methyleth l ether, dipropyl ether and dibutyl ether, the aliphat c ethers o the olyhydroxv alcoho s, such as the dimethyl ether of eth lene glycol, and various amin s such as triethvlamine, aniline, dimethylaniline and diphenylamine.
  • various catal st we have also found that various catal st.
  • reaction starters such as iodine or mercury, often employed to initiate the reaction between the organic halide and the ma nes um, do not interfere with the subsequent use of th h drocarbon-magnesium halide in t e ro ess of our invention.
  • the hydrocarbon-magnesi m halide employed in our in ent on can be pre ared by any one of the wel -known methods.
  • the hydrocarbonmagnesiurn. hal de can be prepar d by the addition to m nesium r et l of a sol tion of an organic h l de in diethyl eth r. and allo ing reaction to take pl ce u til all the magnesium is re acted and dissol e therein, a d then adding this so ution.
  • the ether or other solvent or catalyst emp o ed in the reparation of the hvdrocarbommagnesium halide may be removed by evaporat on and the resulting so id reaction pro uct em loyed in the pro ess of our invention.
  • the amount of solvent or carrier liquid can be varied so as to produce the most efiicient operation.
  • the two-stage embodiment of our invention described in.Example I We have employed, along with the 100 parts of sodiumlead alloy and 167 parts of ethyl chloride of the first stage, 57.4 parts of ethylmagnesium chloride with 22.4, 95.8, 192 and 287 parts of ether and obtained yields of alkyllead product of 56.6, 112, 92.1 and 66.6 parts respectively or 40.3, 83.5, 65.6 and 47.4 percent based on the lead in the sodiumlead alloy.
  • hydrocarbon-magnesium halide can be prepared in the complete absence of the ether or other activating solvent usually associated with the preparation of these compounds. Further, the addition of such solvent to the hydrocarbon-magnesium halide prepared in its absence is likewise not necessary for the successful operation of our process. For example, we prepared ethylmagnesium iodide by treating powdered magnesium with ethyl iodide dissolved in benzene containing a trace of iodine.
  • the process of our invention is not limited to the preparation of tetraalkylead or tetraaryllead compounds in which each of the four alkyl or aryl groups attached to the lead atom is the same, as in tetraethyllead or tetraphenyllead, but also includes the preparation of mixed alkyllead compounds, mixed aryllead compounds and mixed arylalkylead compounds.
  • each of a, b, c, d, and e is a number between and 1 inclusive and the sum as are capab e of forming magnesium salts with the magnesium of the hydrocarbon-magnesium halide, as for example the phosphate radical.
  • the arvlating agent and arylmagnesium halide likewise can be em loyed in the onetare proc ss of Example I but the yield, altho gh m ch higher than that obtained in the pr sent commm al process is somewhat lower than in our -referred t o-sta e embodiment.
  • Th"re was obta ned 119 arts of product or a i ld of 4 5 p r c nt ba e on the l a ha ged a s d um lead a loy S m ar y u in 2% arts of eth l r mide and 862 parts of etL lmaene-s um brom e in 9 .8 parts of eth r in the second stage, the e was obtained 119 narts of r dict or a yield of 34. 5 rer.
  • cent ba ed on the lead in th sodium-l ad allo To llustrate that or th s s fil o rat on of the proce s of o r n ention the ne ati e. or Y. group of the alk lat ng a ent. R'Y. and the X "r up of the h drmar n ma ne i m hal de RJ QX need n t he t e am e on -"ctr? a vo n it -"tn.
  • Example II The importance of the alkylating or arylating agent in combination with the hydrocarbonmagnesium halide of our invention is shown in the following series of operations. 'In one instance the procedure of Example I was followed until the reaction between the ethyl chloride and the sodium-lead alloy was complete, and the product was then discharged from the autoclave and recovered. From 100 parts of sodium-lead alloy was obtained 31.2 parts of product, or a yield of 22.1 per cent based on the lead in the sodiumlead alloy, which is normal for the present commercial process. In a second instance the procedure of Example III was followed with ex- 1 ception that the ethyl chloride was not reintroduced along with the ethylmagnesium chloride and the ether.
  • Example III After the subsequent operations described in Example III the yield of product from per cent based on the lead in the sodium-lead alloy, a result not substantially different from the yield obtained by the present commercial process. As shown in Example III by reintroducing the ethyl chloride along with the ethyl-l L magnesium chloride and the ether a yieldof 117 parts of product or 83.5 per cent was obtained from the 100 parts of sodium-lead alloy.
  • the amount of hydrocarbon-magnesium halide is not critical in the process of our invention.
  • the amount of hydrocarbon-magnesium halide is not critical in the process of our invention.
  • reaction of our process is completed within a few hours, i. e. to 8 hours.
  • a total time within the range of approximately to 6 hours is suflicient.
  • the autoclave is operated under a pressure sufii- 12 cie'ntly high to maintain the fluid reactants in the liquid phase.
  • the pressure in the reaction vessel when using ethyl chloride preferably is maintained within the range of to 150 pounds per square inch gauge.
  • any of the latter container in the final product can be converted to tetraethyllead and free lead by heating.
  • 82% by weight of tetraethyllead is formed and the free lead so produced can be reprocessed.
  • most of the hexaethyldilead can be prevented from forming in our process by employing 100 parts of sodium lead alloy was 81 parts, or 22 ("a temperatures near 85 C. or by leng the time of the reaction at a lower temperature, say 70 C.
  • the reaction zone be free from substantial amounts of certain materials which may be inert and which may act primarily as diluents.
  • certain materials when used in small concentrations are, in some cases, beneficial even though they do not directly improve the yields.
  • certain thermal stabilizers such as diisobutylene, styrene and naphthalene, when added in quantities of the order of a few per cent based on the lead, may be beneficial in reducing the tendency of the alkyllead compounds in the reaction mass to undergo thermal decomposition.
  • accelerators such as acetone, dipropyl lzetone, ethyl acetate, ethyl butyrate and butyl acetate may tend to accelerate the reaction when used in small quantities of the order of .04 part to 1 part of lead. Excessive quantities should be avoided.
  • Hydrocarbons such as commercial gasoline are additional examples of materials which may be beneficial in small quantities, but harmful when used in excess.
  • the presence of such hydrocarbons in substantial amounts tends to interfere with the progress of the alkylation reaction, particularly in the one-stage embodiment of our invention, although relatively small amounts may be of some help.
  • the amount of such hydrocarbons is increased, the yield of tetraalkyllead is reduced until finally little, if any, is produced.
  • a process for making tetraethyllead comprising reacting lead with ethyl chloride and ethylmagnesium chloride.
  • a process for making tetrahydrocarbonlead compounds comprising reacting a lead alloy with an alkylating agent having the hydrocarbon radical in question and having a negative radical which reacts with magnesium and wit an alkylmagnesium halide.
  • a process for making a tetrahydrocarbonlead compound comprising reacting lead with an inorganic acid ester alkylating agent having the hydrocarbon radical in question and having a negative radical which reacts with magnesium and with an alkylmagnesium halide in which the halide is selected from the group consisting of chlorine. bromine and iodine.
  • halide is selected from the group consisting of chlorine, bromine and iodine.
  • a dual process for making tetraethyllead comprising treating a sodium lead alloy with ethyl chloride, and reacting ethyl chloride and 1 ethylmagnesium chloride'with the free lead so formed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US135021A 1949-12-24 1949-12-24 Process for making hydrocarbonlead compounds Expired - Lifetime US2535193A (en)

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Application Number Priority Date Filing Date Title
US135021A US2535193A (en) 1949-12-24 1949-12-24 Process for making hydrocarbonlead compounds
GB9343/50A GB673440A (en) 1949-12-24 1950-04-17 Improvements in or relating to the preparation of tetra-alkyl-and/or-aryl-lead compounds
FR1018934D FR1018934A (fr) 1949-12-24 1950-04-25 Perfectionnements à la préparation de composés plomb-hydrocarbure
DEE1168A DE848817C (de) 1949-12-24 1950-05-12 Verfahren zur Herstellung von Alkyl- bzw. Arylbleiverbindungen

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3234112A (en) * 1961-03-21 1966-02-08 Nalco Chemical Co Process of producing organic lead compounds
US3391066A (en) * 1959-05-06 1968-07-02 Nalco Chemical Co Preparation of organic compounds of metals
US3391067A (en) * 1959-05-06 1968-07-02 Nalco Chemical Co Electrolytic process for the preparation of mixed organic lead compounds and electrolyte therefor
US3431185A (en) * 1964-05-11 1969-03-04 Ethyl Corp Hydrocarbon lead production
US3442923A (en) * 1965-02-04 1969-05-06 Houston Chem Corp Process for the preparation of alkyl lead compounds
US3444223A (en) * 1968-05-20 1969-05-13 Ethyl Corp Production of organolead compounds
US3457288A (en) * 1966-04-13 1969-07-22 Ppg Industries Inc Process for manufacturing tetraorganolead compounds
US3522156A (en) * 1964-10-21 1970-07-28 Ethyl Corp Production of hydrocarbon lead compounds

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3057897A (en) * 1959-01-05 1962-10-09 Ethyl Corp Preparation of organolead compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3391066A (en) * 1959-05-06 1968-07-02 Nalco Chemical Co Preparation of organic compounds of metals
US3391067A (en) * 1959-05-06 1968-07-02 Nalco Chemical Co Electrolytic process for the preparation of mixed organic lead compounds and electrolyte therefor
US3234112A (en) * 1961-03-21 1966-02-08 Nalco Chemical Co Process of producing organic lead compounds
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
US3442923A (en) * 1965-02-04 1969-05-06 Houston Chem Corp Process for the preparation of alkyl lead compounds
US3457288A (en) * 1966-04-13 1969-07-22 Ppg Industries Inc Process for manufacturing tetraorganolead compounds
US3444223A (en) * 1968-05-20 1969-05-13 Ethyl Corp Production of organolead compounds

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FR1018934A (fr) 1953-01-14
GB673440A (en) 1952-06-04
DE848817C (de) 1952-09-08

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