US2454082A - Alkenyl alkali metal compounds - Google Patents
Alkenyl alkali metal compounds Download PDFInfo
- Publication number
- US2454082A US2454082A US622941A US62294145A US2454082A US 2454082 A US2454082 A US 2454082A US 622941 A US622941 A US 622941A US 62294145 A US62294145 A US 62294145A US 2454082 A US2454082 A US 2454082A
- Authority
- US
- United States
- Prior art keywords
- alkali metal
- metal compounds
- alkenyl
- alkyl
- sodium
- 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
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- -1 Alkenyl alkali metal compounds Chemical class 0.000 title description 26
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001339 alkali metal compounds Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000002253 acid Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- ZNXQPKTZYBXOIN-UHFFFAOYSA-N potassium;pentane Chemical compound [K+].CCCC[CH2-] ZNXQPKTZYBXOIN-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- PJISLFCKHOHLLP-UHFFFAOYSA-N 2-diethoxyphosphorylsulfanyl-n,n-diethylethanamine Chemical compound CCOP(=O)(OCC)SCCN(CC)CC PJISLFCKHOHLLP-UHFFFAOYSA-N 0.000 description 1
- NIONDZDPPYHYKY-UHFFFAOYSA-N 2-hexenoic acid Chemical class CCCC=CC(O)=O NIONDZDPPYHYKY-UHFFFAOYSA-N 0.000 description 1
- XKRZDQSVNQTTKA-UHFFFAOYSA-N CC=C[Na] Chemical compound CC=C[Na] XKRZDQSVNQTTKA-UHFFFAOYSA-N 0.000 description 1
- KCMZYCFSSYXEQR-UHFFFAOYSA-N CCCC[K] Chemical compound CCCC[K] KCMZYCFSSYXEQR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- ONQCKWIDZTZEJA-UHFFFAOYSA-N sodium;pentane Chemical compound [Na+].CCCC[CH2-] ONQCKWIDZTZEJA-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
Definitions
- This invention relates to a method of producing alkenyl compounds particularly alkenyl alkali metals and alkenyl carboxylic acids.
- alkyl alkali metal compounds such as alkyl sodium and alkyl potassium
- olefinic hydrocarbons the corresponding alkenyl alkali metal compounds are formed in good yield.
- the reaction is preferably carried out in the presence of an inert liquid medium, such as pentane or other liquid aliphatic hydrocarbons.
- alkenyl alkali metal compounds are readily converted into unsaturated carboxylic acids by treatment with carbon dioxide. This method makes possible the production of a wide variety of unsaturated acids, particularly the heretofore unavailable py-unsaturated carboxylic acids.
- Amylsodium (0.19 mol.) is prepared in the usual manner from amyl chloride and sodium sand in pentane. Isobutene (0.34 mol.) is then added dropwise over a half-hour period at 25 C. Stirring is continued for five hours and the isobutenyl-l-sodium reaction product is then carbonated by passing carbon dioxide into the mixture .for several hours. After carbonation, water is added, the aqueous layer is separated and acidified, and the acid is extracted with petroleum ether. On evaporation of the petroleum ether extract and cooling the pale yellow oil thus obtained to 0., colorless needles of [i-methyl vinylacetio acid are formed, melting at approximately 20 C. and having a refractive index 2.
- Amylpotassium is prepared by the addition over a one-hour period of gm. of amyl chloride, dissolved in 40 ml. of pentane, to 11 gm. of finely divided potassium metal suspended in 200 ml. of pentane at --10 to 15 C. ml. of l-pentene is added at -20 to the amylpotassium thus prepared. The temperature is then allowed to rise to and is maintained there for five hours.
- the 1-pentenyl-3-potassium and l-p-entenyll-potassium thus formed are converted by carbonation into the corresponding hexenoic acids.
- the alkenyl alkali metal compounds can 2 also conveniently be prepared by the reaction of an alkyl halide with an alkali metal in the presence of a liquid olefinic hydrocarbon.
- a liquid olefinic hydrocarbon For example, 30.6 ml. of amyl chloride is added dropwise to a suspension of 11.6 gm. of fine sodium sand in 200 ml. of l-pentene ata temperature of 10 C. over a period of about an hour.
- the reaction mixture is then stirred for about three hours at 2025 C.
- a nearly quantitative yield of 1-pentenyl-3-sodium and l-pentenyl-l-sodium in the proportion of about 4 to 1 is produced.
- alkenyl alkali metals and unsaturated carboxylic acids may be obtained by substituting other olefins, such as l-butene, Z-butene, trimethylethylene and tetram'ethylethylene for the isobutene in Example 1.
- alkyl alkali metals than the amyl compounds specifically referred to in the examples may also be used, for example, butylpotassium.
- alkenyl alkali metal compounds which comprises maintaining an alkali metal compound selected from the group consisting of alkyl sodium and alkyl potassium in intimate admixture with a mono-olefinic aliphatic hydrocarbon containing at least three carbon atoms.
- alkenyl alkali metal compounds which comprises maintaining an alkali metal compound selected from the group consisting of alkyl sodium and alkyl potassium in intimate admixture with a mono-olefinic aliphatic hydrocarbon containing at least three carbon atoms in an inert liquid hydrocarbon.
- the method of making isobutenyl alkali metal compounds which comprises maintaining an alkali metal compounds selected from the group consisting of alkyl sodium and alkyl potassium in intimate admixture with isobutene.
- the method of making isobutenyl alkali metal compounds which comprises maintaining an alkali metal compound selected from the group consisting of alkyl sodium and alkyl potassium in intimate admixture with isobutene in an inert liquid aliphatic hydrocarbon.
- the method of making l-pentenyl alkali metal compounds which comprises maintaining 3 an alkali metal compound selected from the group consisting of alkyl sodium and alkyl potassium in intimate admixture with l-pentene.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Nov. 16, 1948 2,454,082 ALKENYL ALKALI METAL coMroUNns Avery A. Morton, Watertown, Mass, assignor to Research Corporation, New York, N. Y., a corporation of New York No Drawing. Application October 17, 1945, Serial No. 622,941
6 Claims.
This invention relates to a method of producing alkenyl compounds particularly alkenyl alkali metals and alkenyl carboxylic acids.
It has been found that by the reaction of the readily obtained alkyl alkali metal compounds, such as alkyl sodium and alkyl potassium with olefinic hydrocarbons, the corresponding alkenyl alkali metal compounds are formed in good yield. The reaction is preferably carried out in the presence of an inert liquid medium, such as pentane or other liquid aliphatic hydrocarbons.
The alkenyl alkali metal compounds are readily converted into unsaturated carboxylic acids by treatment with carbon dioxide. This method makes possible the production of a wide variety of unsaturated acids, particularly the heretofore unavailable py-unsaturated carboxylic acids.
The invention will be more particularly described with reference to the following examples illustrating the principles of the invention.
1. Amylsodium (0.19 mol.) is prepared in the usual manner from amyl chloride and sodium sand in pentane. Isobutene (0.34 mol.) is then added dropwise over a half-hour period at 25 C. Stirring is continued for five hours and the isobutenyl-l-sodium reaction product is then carbonated by passing carbon dioxide into the mixture .for several hours. After carbonation, water is added, the aqueous layer is separated and acidified, and the acid is extracted with petroleum ether. On evaporation of the petroleum ether extract and cooling the pale yellow oil thus obtained to 0., colorless needles of [i-methyl vinylacetio acid are formed, melting at approximately 20 C. and having a refractive index 2. Amylpotassium is prepared by the addition over a one-hour period of gm. of amyl chloride, dissolved in 40 ml. of pentane, to 11 gm. of finely divided potassium metal suspended in 200 ml. of pentane at --10 to 15 C. ml. of l-pentene is added at -20 to the amylpotassium thus prepared. The temperature is then allowed to rise to and is maintained there for five hours.
The 1-pentenyl-3-potassium and l-p-entenyll-potassium thus formed are converted by carbonation into the corresponding hexenoic acids.
3. The alkenyl alkali metal compounds can 2 also conveniently be prepared by the reaction of an alkyl halide with an alkali metal in the presence of a liquid olefinic hydrocarbon. For example, 30.6 ml. of amyl chloride is added dropwise to a suspension of 11.6 gm. of fine sodium sand in 200 ml. of l-pentene ata temperature of 10 C. over a period of about an hour. The reaction mixture is then stirred for about three hours at 2025 C. A nearly quantitative yield of 1-pentenyl-3-sodium and l-pentenyl-l-sodium in the proportion of about 4 to 1 is produced.
4. By replacing the isobutene in Example 1, by propene, propenylsodium is produced which may be converted to vinylacetic acid by carbonation.
5. correspondingly alkenyl alkali metals and unsaturated carboxylic acids, may be obtained by substituting other olefins, such as l-butene, Z-butene, trimethylethylene and tetram'ethylethylene for the isobutene in Example 1.
Other alkyl alkali metals than the amyl compounds specifically referred to in the examples may also be used, for example, butylpotassium.
I claim:
1. The method of making alkenyl alkali metal compounds which comprises maintaining an alkali metal compound selected from the group consisting of alkyl sodium and alkyl potassium in intimate admixture with a mono-olefinic aliphatic hydrocarbon containing at least three carbon atoms.
2. The method of making alkenyl alkali metal compounds which comprises maintaining an alkali metal compound selected from the group consisting of alkyl sodium and alkyl potassium in intimate admixture with a mono-olefinic aliphatic hydrocarbon containing at least three carbon atoms in an inert liquid hydrocarbon.
3. The method of making isobutenyl alkali metal compounds which comprises maintaining an alkali metal compounds selected from the group consisting of alkyl sodium and alkyl potassium in intimate admixture with isobutene.
4. The method of making isobutenyl alkali metal compounds which comprises maintaining an alkali metal compound selected from the group consisting of alkyl sodium and alkyl potassium in intimate admixture with isobutene in an inert liquid aliphatic hydrocarbon.
5. The method of making l-pentenyl alkali metal compounds which comprises maintaining 3 an alkali metal compound selected from the group consisting of alkyl sodium and alkyl potassium in intimate admixture with l-pentene.
6. The method of making l-pentenyl alkali metal compounds which comprises admixing an alkyl halide with an alkali metal selected from the group consisting of sodium and potassium in the presence of l-pentene and agitating the resulting mixture.
AVERY A. MORTON.
Name Date Morton June 27', 1939 Number Number Name Date 2,171,868 Scott et a1 Sept. 5, 1939 2,352,461 Walker June 27, 1944 2,377,779 Hanford et a1 June 5, 1945 FOREIGN PATENTS Number Country Date 487,727 Germany Jan. 7, 1930 OTHER REFERENCES (Deutsche Chem.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US622941A US2454082A (en) | 1945-10-17 | 1945-10-17 | Alkenyl alkali metal compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US622941A US2454082A (en) | 1945-10-17 | 1945-10-17 | Alkenyl alkali metal compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2454082A true US2454082A (en) | 1948-11-16 |
Family
ID=24496133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US622941A Expired - Lifetime US2454082A (en) | 1945-10-17 | 1945-10-17 | Alkenyl alkali metal compounds |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2454082A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2800559A (en) * | 1953-07-23 | 1957-07-23 | Nat Res Dev | Electrical semi-conductors comprising organo metallic compounds and process of producing same |
| US2848506A (en) * | 1954-04-29 | 1958-08-19 | Hercules Powder Co Ltd | Preparation of cyclopentadienylsodium |
| US2985691A (en) * | 1958-10-06 | 1961-05-23 | Union Carbide Corp | Method of making vinylpotassium |
| US3028406A (en) * | 1955-07-25 | 1962-04-03 | Union Carbide Corp | Preparation of organo-transition element compounds |
| US3185744A (en) * | 1962-04-13 | 1965-05-25 | Procter & Gamble | Process for isomerizing the double bond of straight chain terminal monoolefins |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE487727C (en) * | 1927-12-10 | 1930-01-07 | Karl Ziegler Dr | Process for the production of organic alkali metal compounds |
| US2163846A (en) * | 1936-08-13 | 1939-06-27 | Avery A Morton | Preparation of organosodium compounds |
| US2171868A (en) * | 1936-04-09 | 1939-09-05 | Du Pont | Alkali metal derivatives of acetylenic hydrocarbons |
| US2352461A (en) * | 1942-02-25 | 1944-06-27 | Du Pont | High molecular weight unsaturated organic acids and process of preparing them |
| US2377779A (en) * | 1942-02-18 | 1945-06-05 | Du Pont | Process for polymerizing ethylene |
-
1945
- 1945-10-17 US US622941A patent/US2454082A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE487727C (en) * | 1927-12-10 | 1930-01-07 | Karl Ziegler Dr | Process for the production of organic alkali metal compounds |
| US2171868A (en) * | 1936-04-09 | 1939-09-05 | Du Pont | Alkali metal derivatives of acetylenic hydrocarbons |
| US2163846A (en) * | 1936-08-13 | 1939-06-27 | Avery A Morton | Preparation of organosodium compounds |
| US2377779A (en) * | 1942-02-18 | 1945-06-05 | Du Pont | Process for polymerizing ethylene |
| US2352461A (en) * | 1942-02-25 | 1944-06-27 | Du Pont | High molecular weight unsaturated organic acids and process of preparing them |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2800559A (en) * | 1953-07-23 | 1957-07-23 | Nat Res Dev | Electrical semi-conductors comprising organo metallic compounds and process of producing same |
| US2848506A (en) * | 1954-04-29 | 1958-08-19 | Hercules Powder Co Ltd | Preparation of cyclopentadienylsodium |
| US3028406A (en) * | 1955-07-25 | 1962-04-03 | Union Carbide Corp | Preparation of organo-transition element compounds |
| US2985691A (en) * | 1958-10-06 | 1961-05-23 | Union Carbide Corp | Method of making vinylpotassium |
| US3185744A (en) * | 1962-04-13 | 1965-05-25 | Procter & Gamble | Process for isomerizing the double bond of straight chain terminal monoolefins |
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