US2594183A - Manufacture of alkyllead compounds with calcium-lead alloys - Google Patents
Manufacture of alkyllead compounds with calcium-lead alloys Download PDFInfo
- Publication number
- US2594183A US2594183A US229001A US22900151A US2594183A US 2594183 A US2594183 A US 2594183A US 229001 A US229001 A US 229001A US 22900151 A US22900151 A US 22900151A US 2594183 A US2594183 A US 2594183A
- Authority
- US
- United States
- Prior art keywords
- calcium
- lead
- alloy
- manufacture
- alkyllead
- 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
Links
- 150000001875 compounds Chemical class 0.000 title description 8
- 229910000978 Pb alloy Inorganic materials 0.000 title description 3
- PRSMTOHTFYVJSQ-UHFFFAOYSA-N [Ca].[Pb] Chemical compound [Ca].[Pb] PRSMTOHTFYVJSQ-UHFFFAOYSA-N 0.000 title description 2
- 238000004519 manufacturing process Methods 0.000 title description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000002168 alkylating agent Substances 0.000 claims description 9
- 229940100198 alkylating agent Drugs 0.000 claims description 9
- 239000002142 lead-calcium alloy Substances 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 16
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 3
- 229960003750 ethyl chloride Drugs 0.000 description 3
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical class CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- WBLCSWMHSXNOPF-UHFFFAOYSA-N [Na].[Pb] Chemical compound [Na].[Pb] WBLCSWMHSXNOPF-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- OLOAJSHVLXNSQV-UHFFFAOYSA-N diethyl(dimethyl)plumbane Chemical compound CC[Pb](C)(C)CC OLOAJSHVLXNSQV-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012021 ethylating agents Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- XOOGZRUBTYCLHG-UHFFFAOYSA-N tetramethyllead Chemical compound C[Pb](C)(C)C XOOGZRUBTYCLHG-UHFFFAOYSA-N 0.000 description 1
- SMHNCYOTIYFOKL-UHFFFAOYSA-N tetrapropylplumbane Chemical compound CCC[Pb](CCC)(CCC)CCC SMHNCYOTIYFOKL-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- KGFRUGHBHNUHOS-UHFFFAOYSA-N triethyl(methyl)plumbane Chemical compound CC[Pb](C)(CC)CC KGFRUGHBHNUHOS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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 new process for making alkyllead compounds.
- alkyllead compounds The most important of the alkyllead compounds is tetraethyllead which is made commercially by reacting monosodium-lead alloy with ethyl chloride in accordance with the following equation This process has been successful but it has certain disadvantages since three-fourths of the lead is not utilized in the reaction.
- the usual yield of tetraethyllead is only about 22 weight per cent based on the lead.
- the above object is accomplished by reacting an alkylating agent with a particular calciumlead alloy composition.
- a particular calciumlead alloy composition We have found that not all calcium alloys of lead are reactive. For instance, we have found that no alkyllead is formed from an alloy composition having an atom ratio of calcium to lead or 2 to l which corresponds to the formula CaaPb. This alloy is unreactive al though from a theoretical viewpoint it is the most desirable alloy since no free lead would be formed according to the reaction which may be expressed as follows:
- R is an alkyl radical
- R is an alkyl radical and X is an inorganic acid radical which reacts with calcium to form a salt.
- any of the allrylating agents heretofore used or described in the prior art can be used, among which are the alltyl halides preferably the iodides, bromides and chlorides, the dialkyl sulfates and the trialkyl phosphates.
- the alkylating agents are esters of inorganic acids having the proper alkyl groups for making the desired alkyllead compound, and having an inorganic acid group which forms a salt with calcium,
- those which can be used in our invention are the ethyl, propyl and butyl chlorides, as well a the corresponding bromides and iodides, diethylsulfate and triethylphosphate.
- tetraethyllead is the principal compound discussed herein because of its large commercial use
- alkyllead compounds such as tetramethyllead, tetrapropyllead, dimethyldiethyllead and methyltriethyllead can be made by the process of our invention.
- the temperature employed is not important, thepreferablerange being 50 to 100 C.
- the pressure used is not critical but should be sufficient at the temperature employed to maintain the alkyl-- ating agent in the liquid phase.
- the time of reaction is between about 30 minutes and 8 hours.
- the amount of alkylating agent employed is not critical but an excess over the stoichiometric amount is preferred.
- Example I A charge of 100 parts of calcium lead alloy having an atomic ratio of calcium to lead about 1 to 1 is added to the 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 209 parts is added under pressure to the stirred solids in the vessel over a period of one-half hour. By controlling the flow of liquid in the autoclave jacket and in the reflux condenser the temperature of the reaction mass is permitted to rise from an initial temperature of 50 C. to a temperature of C. during this feed period. The pressure in the autoclave during this feed rises to pounds per square inch gauge where it is maintained.
- the temperature of the stirred reaction mixture is maintained at 70 C. for about 5 hours at the end of which the pressure is reduced to atmospheric and the reaction mass removed and charged to a steam still wherein the alkyllead product is recovered.
- the yield of tetraethyllead is 52 parts or 40 per cent based on the lead present in the calcium lead alloy.
- catalysts of-the carbonyl type substantially improves the results obtained.
- catalysts are the ketones, aldehydes, acid anhydrides, esters and other derivatives of carboxylic acids.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented 22, 1952 MANUFACTURE OF ALKYLLEAD COM- POUNDS WITH CALCIUM-LEAD ALLOYS livar T. Krohn, Royal Oak, and Hymin Shapiro, Detroit, Mich, assignors to Ethyl Corporation, New York, N. Y., a corporation of Delaware ,No Drawing. Application May 29, 1951, Serial No. 229,001
4 Claims.
This invention relates to a new process for making alkyllead compounds.
The most important of the alkyllead compounds is tetraethyllead which is made commercially by reacting monosodium-lead alloy with ethyl chloride in accordance with the following equation This process has been successful but it has certain disadvantages since three-fourths of the lead is not utilized in the reaction. The usual yield of tetraethyllead is only about 22 weight per cent based on the lead.
Among the objects of our invention is to provide a process in which the yield of tetraethyllead is higher than that obtained in the present process.
The above object is accomplished by reacting an alkylating agent with a particular calciumlead alloy composition. We have found that not all calcium alloys of lead are reactive. For instance, we have found that no alkyllead is formed from an alloy composition having an atom ratio of calcium to lead or 2 to l which corresponds to the formula CaaPb. This alloy is unreactive al though from a theoretical viewpoint it is the most desirable alloy since no free lead would be formed according to the reaction which may be expressed as follows:
in which R is an alkyl radical.
We have made the surprising discovery that high yields of alkyllead compounds based on the lead charged are made by an alloy in which the atomic ratio of calcium to lead is between about 1 to 1 and 1.5 to 1 and particularly with a composition consisting essentially of one atom of calcium for one atom of lead as expressed by the formula CaPb. The reaction between this alloy and an alkylating agent can be expressed as follows:
in which R is an alkyl radical and X is an inorganic acid radical which reacts with calcium to form a salt.
Any of the allrylating agents heretofore used or described in the prior art can be used, among which are the alltyl halides preferably the iodides, bromides and chlorides, the dialkyl sulfates and the trialkyl phosphates. In general, the alkylating agents are esters of inorganic acids having the proper alkyl groups for making the desired alkyllead compound, and having an inorganic acid group which forms a salt with calcium, Among those which can be used in our invention are the ethyl, propyl and butyl chlorides, as well a the corresponding bromides and iodides, diethylsulfate and triethylphosphate.
While tetraethyllead is the principal compound discussed herein because of its large commercial use, other alkyllead compounds such as tetramethyllead, tetrapropyllead, dimethyldiethyllead and methyltriethyllead can be made by the process of our invention.
The temperature employed is not important, thepreferablerange being 50 to 100 C. The pressure used is not critical but should be sufficient at the temperature employed to maintain the alkyl-- ating agent in the liquid phase. The time of reaction is between about 30 minutes and 8 hours. The amount of alkylating agent employed is not critical but an excess over the stoichiometric amount is preferred.
Our invention can be best understood by referring to the following typical working examples in which all the parts are by weight and the percentages are by weight based on the lead charged.
Example I A charge of 100 parts of calcium lead alloy having an atomic ratio of calcium to lead about 1 to 1 is added to the 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 209 parts is added under pressure to the stirred solids in the vessel over a period of one-half hour. By controlling the flow of liquid in the autoclave jacket and in the reflux condenser the temperature of the reaction mass is permitted to rise from an initial temperature of 50 C. to a temperature of C. during this feed period. The pressure in the autoclave during this feed rises to pounds per square inch gauge where it is maintained. The temperature of the stirred reaction mixture is maintained at 70 C. for about 5 hours at the end of which the pressure is reduced to atmospheric and the reaction mass removed and charged to a steam still wherein the alkyllead product is recovered. The yield of tetraethyllead is 52 parts or 40 per cent based on the lead present in the calcium lead alloy.
' Similarly when ethyl iodide or ethyl bromide are substituted in the above example, keeping all the conditions the same, substantially the 55 same yields are obtained, slightly higher yields being obtained with ethyl iodide. Also when the temperature of the reaction is raised to 85 C. substantially the same yield is obtained.
However, when the atomic ratio of calcium to lead was changed to about 2 to 1, which corresponds to the theoretical desirable composition of CazPb, no yield of tetraethyllead was obtained.
Thus, almost a two-fold yield over that obtained in the present commercial process is-made by our process in which the atomic ratio of calcium to lead is about 1 to 1.
In other examples when theatomic :ratio of calcium to lead was increasedtoaboutliiy-substantial yields of tetraethylleadwere-obtained;
Furthermore certain catalysts of-the carbonyl type substantially improves the results obtained. Among such catalysts are the ketones, aldehydes, acid anhydrides, esters and other derivatives of carboxylic acids.
Other embodimentsof our invention can be made without departing from the spirit and scope of ourinvention which isnot limited to specific embodiments given herein.
We claim:
1. The process for making Shydrocarbon-lead compounds "comprising reacting a calcium-lead alloy consisting" essentially of an alloy'having an atomic ratio of calcium to lead between about 1 to l and 1.5 to 1 with an alkylating agent which includes the hydrocarbon radical in question and having a negative radical which reacts with calcium.
3. The process of claim 1 for making tetrae-thyllead in which the alkylating agent is an ethylating agent.
4. The process of claim 1 for making tetraethyllead in which the alkylating agent is ethyl chloride.
IVAR T. KROHN. HYMIN SHAPIRO.
Hansen -Der 'Au'fbau der Zweistofilegieriengen, Edwards Bros. Inc., Ann Arbor, Michigan, 1943, pages 403-404.
Number 2 535,237
2. 'The process of claim'l'inwhich the atomic V ratio of calcium" to lead is about 1 to 1.
Claims (1)
1. THE PROCESS FOR MAKING HYDROCARBON-LEAD COMPOUNDS COMPRISING REACTING A CALCIUM-LEAD ALLOY CONSISTING ESSENTIALLY OF AN ALLOY HAVING AN ATOMIC RATIO OF CALCIUM TO LEAD BETWEEN ABOUT 1 TO 1 AND 1.5 TO 1 WITH AN ALKYLATING AGENT WHICH INCLUDES THE HYDROCARBON RADICAL IN QUESTION AND HAVING A NEGATIVE RADICAL WHICH REACTS WITH CALCIUM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US229001A US2594183A (en) | 1951-05-29 | 1951-05-29 | Manufacture of alkyllead compounds with calcium-lead alloys |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US229001A US2594183A (en) | 1951-05-29 | 1951-05-29 | Manufacture of alkyllead compounds with calcium-lead alloys |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2594183A true US2594183A (en) | 1952-04-22 |
Family
ID=22859427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US229001A Expired - Lifetime US2594183A (en) | 1951-05-29 | 1951-05-29 | Manufacture of alkyllead compounds with calcium-lead alloys |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2594183A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2535237A (en) * | 1948-05-29 | 1950-12-26 | Ethyl Corp | Preparation of tetraalkyllead |
-
1951
- 1951-05-29 US US229001A patent/US2594183A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2535237A (en) * | 1948-05-29 | 1950-12-26 | Ethyl Corp | Preparation of tetraalkyllead |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2680758A (en) | Dicyclopentadienylnickel and method | |
| US3085102A (en) | Process for producing alkyl tin halide compounds | |
| US2436141A (en) | Dialkyl esters of long-chain alkylphosphonates | |
| US2754320A (en) | Production of diesterified phosphono derivatives of monofunctional compounds | |
| US2862952A (en) | Method of preparing b-hydrocarbonsubstituted boron compounds | |
| US3061647A (en) | Process for producing metal organic compounds | |
| US2594183A (en) | Manufacture of alkyllead compounds with calcium-lead alloys | |
| US2594225A (en) | Manufacture of alkyllead compounds with calcium-lead alloys | |
| US2558207A (en) | Manufacture of alkyllead compounds | |
| US2763665A (en) | Process for the manufacture of levulinic acid esters | |
| FREY Jr et al. | Bimetallic Ethyl Compounds as Reagents for the Synthesis of Tetraethyllead from Lead Metal | |
| DE870412C (en) | Process for the production of organosilanes | |
| US2591509A (en) | Manufacture of alkyl lead compounds | |
| US2987534A (en) | Group iii-a element compounds | |
| US2562856A (en) | Manufacture of alkyllead compounds | |
| US3071607A (en) | Vinyllead compounds | |
| US2878255A (en) | Dixylyl phosphoramidates | |
| US2575323A (en) | Manufacture of organolead compounds | |
| US3072697A (en) | Process for producing organolead compounds | |
| US2848471A (en) | Preparation of tetraethyl lead | |
| US2535192A (en) | Manufacture of alkyllead compounds | |
| US2082568A (en) | Vinylethinyl derivatives and processes for producing same | |
| US3188345A (en) | B-halo phosphine borines | |
| GB673871A (en) | Improvements in or relating to process for the manufacture of tetraalkyllead compounds | |
| US3030375A (en) | Novel borated compounds |