US1611695A - Manufacture of lead alkyl compounds - Google Patents
Manufacture of lead alkyl compounds Download PDFInfo
- Publication number
- US1611695A US1611695A US742063A US74206324A US1611695A US 1611695 A US1611695 A US 1611695A US 742063 A US742063 A US 742063A US 74206324 A US74206324 A US 74206324A US 1611695 A US1611695 A US 1611695A
- Authority
- US
- United States
- Prior art keywords
- lead
- sodium
- sulfate
- mixture
- tetraethyl
- 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
- 125000000217 alkyl group Chemical group 0.000 title description 6
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000000203 mixture Substances 0.000 description 14
- 229910000978 Pb alloy Inorganic materials 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 11
- 229940008406 diethyl sulfate Drugs 0.000 description 11
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical group CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 11
- WBLCSWMHSXNOPF-UHFFFAOYSA-N [Na].[Pb] Chemical compound [Na].[Pb] WBLCSWMHSXNOPF-UHFFFAOYSA-N 0.000 description 10
- 229910052736 halogen Inorganic materials 0.000 description 10
- 150000002367 halogens Chemical class 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 150000004820 halides Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 150000008050 dialkyl sulfates Chemical class 0.000 description 3
- 150000002366 halogen compounds Chemical class 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- RJFAYQIBOAGBLC-BYPYZUCNSA-N Selenium-L-methionine Chemical compound C[Se]CC[C@H](N)C(O)=O RJFAYQIBOAGBLC-BYPYZUCNSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- SURLGNKAQXKNSP-DBLYXWCISA-N chlorin Chemical compound C\1=C/2\N/C(=C\C3=N/C(=C\C=4NC(/C=C\5/C=CC/1=N/5)=CC=4)/C=C3)/CC\2 SURLGNKAQXKNSP-DBLYXWCISA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- MXCPYJZDGPQDRA-UHFFFAOYSA-N dialuminum;2-acetyloxybenzoic acid;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3].CC(=O)OC1=CC=CC=C1C(O)=O MXCPYJZDGPQDRA-UHFFFAOYSA-N 0.000 description 1
- LMEDOLJKVASKTP-UHFFFAOYSA-N dibutyl sulfate Chemical compound CCCCOS(=O)(=O)OCCCC LMEDOLJKVASKTP-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- JKLNYGDWYRKFKR-UHFFFAOYSA-N ethyl methyl sulfate Chemical compound CCOS(=O)(=O)OC JKLNYGDWYRKFKR-UHFFFAOYSA-N 0.000 description 1
- IKMUGMBLZVUWBF-UHFFFAOYSA-N ethyl propyl sulfate Chemical compound CCCOS(=O)(=O)OCC IKMUGMBLZVUWBF-UHFFFAOYSA-N 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- -1 zinc halides Chemical class 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
- the invention will be specifically dccribed in connection with the manufacture of lead tetra'ethyl, although, as hereinafter pointed out, other lead alkyl compounds maybe manufactured under the process of thls invention.
- a sodium lead alloy is subjected tothe action ofethyl sulfate, preferably vii -the presence of a halogen containing ganic halide.
- Thesodium' lead alloy may preferred that its sodi-liih contents be within the range'of from "li to 20%.
- the alloy containing 10% of s odiu'm has been found; to be particularly suitable;
- the amount of dietliyl sulfate employed is preferably not in excess of the calculaped equivalent 'required for reaction with the lead alloy, only one ethyl group being considered as reactive,
- the cal-- (lulated equivalent quantity 'of diethyl sulfate is about 67 parts.
- the use of rts has been found to be particularlya vantageous, although lower. or higher proporene-r-j' tions may be employed. It is not allydesirable thatthe proportion of diethyl sulfate employed be less than 50% of the calculated equivalent.
- Anon-aqueous solventsu'ch as benzol, toluol or the like may be employed, serving primarilyjto control the rate of reaction. -It is also desirable that a, slight trace of Water be present;
- the reactlonco i s tituents are admixed, pref-o I erabl-y with the solvent, the proportion of- .which, *whenused 'amount equal in, weightflto the amount of ethyl sulfate to from 50toj100% more and 'a tracefiof water, aytwklifto three reps may be added.
- mixture is then' heated to boiling under al refluxcondenser under pressure while hemg stirred until reaction 1 is completed to small amount of a ed.
- chlorine chlorine
- halogen catalyst be ad vcompound, preferably .an inorparts oflead tetraethyl, a yield of approx- ,may vary from an Application filed October 6, 1924. Serial No. 742,063.
- bromine, iodine, or their salts such as the alkali metal, alkaline earth metal, and zinc halides and the like may be employed.
- tent of the mixture being The following specific instance of a proc ess carried out under this invention illus trates'satisfactory conditions for operation.
- T 1e invention mav be employedsin ma'nucomprising admixing a. so im lead alloyiodine compound ture of a sodium lead allo and a dialkyl sulfate, and the subsequent eating of the mixture. a. so im lead alloyiodine compound ture of a sodium lead allo and a dialkyl sulfate, and the subsequent eating of the mixture. a. so im lead alloyiodine compound ture of a sodium lead allo and a dialkyl sulfate, and the subsequent eating of the mixture. a. so im lead alloyiodine compound ture of a sodium lead allo and a dialkyl sulfate, and the subsequent eating of the mixture. a. so im lead alloyiodine compound ture of a sodium lead allo and a dialkyl sulfate, and the subsequent eating of the mixture. a. so im lead alloyiodine compound ture of a sodium lead allo and a dialkyl
- the method pounds comprising admixing a sodium lead alloy and a dialkyl sulfate in the presence of a halogen compound derived from the group including the elemental halogens and the soluble metallic halides and heating the mixture.
- the method of forming lead tetraethyl comprising admixing a sodium-lead alloy containing 3 to 31% of sodium with at least 50% .of the monomolecular' equivalent of diethyl sulfate and heating the mixture.
- the method of forming lead tetraethyl comprising admixing 100 parts of a sodium lead alloy containing 1( of sodium, 50 parts of diethyl sulfate, 'pa1-t of potassium iodide, about 65 parts of toluol and a trace of water an'd heating the mixture un reflux condenser. 7
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Dec. 1926.
.A-UNITED v sT rEs PATENT fol-rice.
rnnnnnrox w. SULLIVAN, .13., AND LYMAN' CHALKLEY, .13., or wnrrme, IN IANA, nssreuons 'ro smunann OIL COMPANY, or WRITING, INDIANA, A CORPORATION OF INDIANA.
MANUFACTURE or. LEAD 'ALKYL' controuuns.
' No Drawing.
pounds, "and more particularly of 'lead.
. contain from 3 to 317aof sodium, 'it being,
\ the desired extent.
or may be heated tetraethyl, and will be fully understood from the 'followin description thereof. r
The invention will be specifically dccribed in connection with the manufacture of lead tetra'ethyl, although, as hereinafter pointed out, other lead alkyl compounds maybe manufactured under the process of thls invention. I l r ln'carrying out the invention for the for .mation of lead tetra/ethyl, a sodium lead alloy is subjected tothe action ofethyl sulfate, preferably vii -the presence of a halogen containing ganic halide. Thesodium' lead alloy may preferred that its sodi-liih contents be within the range'of from "li to 20%. The alloy containing 10% of s odiu'm has been found; to be particularly suitable; The amount of dietliyl sulfate employed is preferably not in excess of the calculaped equivalent 'required for reaction with the lead alloy, only one ethyl group being considered as reactive, Thus for .100 parts of sodiumlead alloy containing 10% of sodium, the cal-- (lulated equivalent quantity 'of diethyl sulfate is about 67 parts. The use of rts has been found to be particularlya vantageous, although lower. or higher proporene-r-j' tions may be employed. It is not allydesirable thatthe proportion of diethyl sulfate employed be less than 50% of the calculated equivalent. Anon-aqueous solventsu'ch as benzol, toluol or the like may be employed, serving primarilyjto control the rate of reaction. -It is also desirable that a, slight trace of Water be present;
The reactlonco i s tituents are admixed, pref-o I erabl-y with the solvent, the proportion of- .which, *whenused 'amount equal in, weightflto the amount of ethyl sulfate to from 50toj100% more and 'a tracefiof water, aytwklifto three reps may be added. mixture is then' heated to boiling under al refluxcondenser under pressure while hemg stirred until reaction 1 is completed to small amount of a ed. Thus chlorine,
It is preferred that halogen catalyst be ad vcompound, preferably .an inorparts oflead tetraethyl, a yield of approx- ,,may vary from an Application filed October 6, 1924. Serial No. 742,063.
bromine, iodine, or their salts, such as the alkali metal, alkaline earth metal, and zinc halides and the like may be employed. The
proportion required is very small, in general from one-halftothre'e per cent based on the diethyl sulfate con sufi'icient. With potassium iodide as a catalyst, highly satisfactory results have been obtained employing 1%..-
tent of the mixture being The following specific instance of a proc ess carried out under this invention illus trates'satisfactory conditions for operation.
100 parts of' ing 10% of sodium, 50 parts of ethyl sulsodium lead alloy containfate and about {parts of toluol are thoroughly mixed, 0.5 parts potassium iodide and-a. traze of water (two or three drops) being added. The mixture is boiled under a reflux column while being stirred, the"- heating being continued until'the reaction is carried to substantial completiom h'om 4 to 6 hours being required. In order to separate the lead tetraethyl produced, the re action mixture is treated with Water, and distilled or the lead tetraethyl otherwise re-' The separation may be or I vacuum distillation,
imately of theoretical, arejobtamecl. Th
which potassium iodide isan. example,
. P- pears greatly accelerate the rate of re I action and increase the yield. 7 The reaction may be carried out; however, without such facturing other lead alkyl compounds, 'sub-. stituting for the diethyl sulfate other alkyl sulfates' such as dimethyl sulfate, dipropyl sulfate,
ethylmethyl sulfate,
ethyl propyl sulfate, dibutyl sulfate and the like, the proportion of the various constituents 'of the as indicated with th man ufacture reaction mixture being varied above in connection of'lead tetraethyl. K .lVe claim: 3
1. The method of manufacturing lead alkyl compounds comprising the intermixe presence of a halide catalyst, 'ofw as chlorin, bromin,
T 1e invention mav be employedsin ma'nucomprising admixing a. so im lead alloyiodine compound ture of a sodium lead allo and a dialkyl sulfate, and the subsequent eating of the mixture. a
2. The method pounds comprising admixing a sodium lead alloy and a dialkyl sulfate in the presence of a halogen compound derived from the group including the elemental halogens and the soluble metallic halides and heating the mixture. x
3. The method of forming a lead alkyl comprising admixing a sodium lead alloy and a dialkyl sulfate in theresence of a halogen compound derived rom the group including the elemental halogens and the soluble metallic halides and a trace of Water, and heatin the mixture.
4. The method forming lead tetraethyl comprising admixing and heating together a sodium lead alloy and diethyl sulfate.
5'. The method of forming lead tetraethyl comprising admixing a sodium lead alloy and diethyl sulfate in the presence of a halogen compound derived from the group including the elemental halogens and the soluble metallic halides and heatingthe mixture.
6. The method of forming lead tetraethyl comprising admixing a sodium lead alloy and diethyl sulfatein' the presence of an derived from the group including iodine and the soluble metallic iodides and a trace of water and'heating the mixture.
Y 7. The method of forinin lead tetraethyl of forming lead alkyl com-- with diethyl sulfate in the presence'of an anhydrous solvent and a halogen catalyst derived from the group including the elemental halogens and the soluble metallic halides, and heating the mixture. 8. The method of forming lead tetraethyl comprising admixing a-sodium lead alloy with diethyl sulfate in amounts not in excess of the monomolecular equivalent, incorporating in the mixture a halogen catalyst derived from the group including the elemental halogens and the soluble metallic halides and heating'themixture.
9". The method of forming lead tetraethyl comprising admixing a sodium-lead alloy containing 3 to 31% of sodium with at least 50% .of the monomolecular' equivalent of diethyl sulfate and heating the mixture.
10. The method of forming lead tetraethyl compi'ising admixing? a sodium lead alloy containing 3 to 31% of sodium With at vleast 50% of the monomolecular equivalent of diethyl sulfate in the presence of a halogen body derived'from the group includingthe elemental halogensand the soluble metallic halides and'a tr'a'ce of water, and heating the mixture. 5 j
11. The method of forming lead tetraethyl comprising admixing 100 parts of a sodium lead alloy containing 1( of sodium, 50 parts of diethyl sulfate, 'pa1-t of potassium iodide, about 65 parts of toluol and a trace of water an'd heating the mixture un reflux condenser. 7
Y FREDERICK w. SULLIVAN, JR;- Li M N enAnm. 1 a r ..-IR.-
dera"
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US742063A US1611695A (en) | 1924-10-06 | 1924-10-06 | Manufacture of lead alkyl compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US742063A US1611695A (en) | 1924-10-06 | 1924-10-06 | Manufacture of lead alkyl compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1611695A true US1611695A (en) | 1926-12-21 |
Family
ID=24983353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US742063A Expired - Lifetime US1611695A (en) | 1924-10-06 | 1924-10-06 | Manufacture of lead alkyl compounds |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1611695A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2621199A (en) * | 1951-04-30 | 1952-12-09 | Ethyl Corp | Production of lead alkyls |
| US2688628A (en) * | 1951-11-27 | 1954-09-07 | Ethyl Corp | Manufacture of alkyllead compounds |
| US2727053A (en) * | 1951-11-23 | 1955-12-13 | Ethyl Corp | Manufacture of alkyllead compounds |
| US2982778A (en) * | 1958-02-03 | 1961-05-02 | Ethyl Corp | Manufacture of tetraethyllead |
| US3113955A (en) * | 1961-08-17 | 1963-12-10 | Du Pont | Process for making tetramethyl lead |
| US3197491A (en) * | 1961-02-07 | 1965-07-27 | Du Pont | Process for making tetraethyl lead |
-
1924
- 1924-10-06 US US742063A patent/US1611695A/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2621199A (en) * | 1951-04-30 | 1952-12-09 | Ethyl Corp | Production of lead alkyls |
| US2727053A (en) * | 1951-11-23 | 1955-12-13 | Ethyl Corp | Manufacture of alkyllead compounds |
| US2688628A (en) * | 1951-11-27 | 1954-09-07 | Ethyl Corp | Manufacture of alkyllead compounds |
| US2982778A (en) * | 1958-02-03 | 1961-05-02 | Ethyl Corp | Manufacture of tetraethyllead |
| US3197491A (en) * | 1961-02-07 | 1965-07-27 | Du Pont | Process for making tetraethyl lead |
| US3113955A (en) * | 1961-08-17 | 1963-12-10 | Du Pont | Process for making tetramethyl lead |
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