US3373192A - Preparation of alkane sulfonyl chlorides from trialkylaluminum and sulfuryl chloride - Google Patents
Preparation of alkane sulfonyl chlorides from trialkylaluminum and sulfuryl chloride Download PDFInfo
- Publication number
- US3373192A US3373192A US834958A US83495859A US3373192A US 3373192 A US3373192 A US 3373192A US 834958 A US834958 A US 834958A US 83495859 A US83495859 A US 83495859A US 3373192 A US3373192 A US 3373192A
- Authority
- US
- United States
- Prior art keywords
- trialkylaluminum
- sulfuryl chloride
- alkane sulfonyl
- preparation
- reaction
- 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
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 title claims description 16
- 238000002360 preparation method Methods 0.000 title claims description 7
- 125000004390 alkyl sulfonyl group Chemical group 0.000 title description 11
- 238000000034 method Methods 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 17
- -1 ALUMINUM COMPOUND Chemical class 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 241001647090 Ponca Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 2
- XBEXIHMRFRFRAM-UHFFFAOYSA-N tridodecylalumane Chemical compound CCCCCCCCCCCC[Al](CCCCCCCCCCCC)CCCCCCCCCCCC XBEXIHMRFRFRAM-UHFFFAOYSA-N 0.000 description 2
- FPTXIDMSUMCELA-UHFFFAOYSA-N trioctadecylalumane Chemical compound CCCCCCCCCCCCCCCCCC[Al](CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC FPTXIDMSUMCELA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical class O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
Definitions
- Suitable trialkylaluminum compounds include trimethyl, triethyl, tripropyl, etc., aluminum compounds. I prefer to employ trialkylaluminum compounds wherein the alkyl group contains from 6 to 18 carbon atoms, but compounds can be used wherein the alkyl group contains a larger number of carbon atoms. In addition to trialkylaluminum compounds, other aluminum organo compounds may be used, such as those identified by the general formulas AlR C1 and R AlOR wherein the Rs represent alkyl radicals containing from 1 to 18 or more carbon atoms. The alkyl groups of these compounds may be the same or diflerent.
- Suitable solvents for dissolving the trialkylaluminum compound and the sulfuryl chloride include aromatic and aliphatic hydrocarbons and ethers. I prefer to employ a solvent that has a boiling point sutiiciently low so that it can be readily removed from the other components in the reaction mixture by distillation but high enough that losses through evaporation are not excessive. Also, if the solvent has low boiling point it will form explosive mix tures with air readily and as a consequence the use of such a compound can be hazardous. As a rule, suitable solvents are those having boiling points within the range of about 30 to 200 C. I prefer to use solvents having boiling points within the range of about 40 to C. Preferred solvents are the hydrocarbons, and it is not necessary to use a pure hydrocarbon, however, as mixtures are satisfactory.
- the temperature of operation that may vary from about 25 to C.
- the time of reaction that is very rapid and varies inversely as temperature and varies from a few seconds to several hours. Specifically, when a reaction tempera ture of 100 is employed, the reaction is complete in a few seconds. On the other hand, if the reaction temperature is 25" C., several hours time will be required for the reaction to go to completion. When the process is operated within the preferred temperature range (0 to 30 C.), the time of reaction varies from 15 minutes to 2 hours.
- the reaction is carried out in the absence of air, and this is accomplished by maintaining the entire reaction under an atmosphere of an inert gas.
- gases for this purpose include any gas that will not react with any of the reactants present. This will include the noble gases and nitrogen.
- parts by weight bear the same relation to parts by volume as do grams to cubic centimeters.
- Example 1 A solution of 161 parts by weight of sulfuryl chloride dissolved in 200 parts by volume of hexane was placed in a reaction vessel. After the air in the reaction vessel was replaced with nitrogen, 260 parts by weight of trioctylaluminum was added thereto slowly with stirring while the temperature was maintained between 15 to -25 C. After the addition was completed, the reaction mixture was allowed to stand /2 hour at room temperature and then the aqueous layer extracted with 100 parts by volume of hexane. The hexane was removed under a vacuum and the l-octanesulfonyl chloride recovered in a yield of 75% of theory. Analysis of the recovered product showed that the chlorine content was 16.06% as contrasted to theoretical chlorine content of 16.71%. It exhibited characteristic infrared absorption bands at 7.25 and 8.56 microns.
- Example 2 A solution of 96 parts by weight of sulfuryl chloride dissolved in parts of hexane was placed in a reaction vessel. After the air was replaced with nitrogen 240 parts 3 by weight of trioctadecylaluminum was added to the contents in the reaction vessel. The procedure was similar to the procedure used in Example 1 with the exception that the temperature was maintained within a range of to 25 C. In the end of the reaction, the reaction mixture was poured onto 400 parts by weight of ice producing a white precipitate. The mixture was heated on a steam bath and hexane was added until the precipitate dissolved.
- the hexane layer was separated and, after cooling and evaporating the hexane, l-octadecanesulfonyl chloride was obtained in a good yield. Analysis of this product showed that it contained 9.95% chlorine as against 10.07% on a calculated basis. The product exhibited characteristic infrared absorption bands at 7.35 and 8.65 microns.
- a process for the preparation of an alkane sulfonyl chloride which comprises reacting a trialkylaluminum compound with sulfuryl chloride wherein the alkyls in said alkyl aluminum compound contains from 1-18 carbon atoms therein, and wherein said trialkylaluminum compound is added under an atmosphere of an inert gas to sulfuryl chloride at a temperature within the range of 25 to 100 C. in the presence of an inert organic solvent, cooling the resultant reaction mixture, and then recovering the alkane sulfonyl chloride.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL254277D NL254277A (enrdf_load_stackoverflow) | 1959-08-20 | ||
| US834958A US3373192A (en) | 1959-08-20 | 1959-08-20 | Preparation of alkane sulfonyl chlorides from trialkylaluminum and sulfuryl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US834958A US3373192A (en) | 1959-08-20 | 1959-08-20 | Preparation of alkane sulfonyl chlorides from trialkylaluminum and sulfuryl chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3373192A true US3373192A (en) | 1968-03-12 |
Family
ID=25268213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US834958A Expired - Lifetime US3373192A (en) | 1959-08-20 | 1959-08-20 | Preparation of alkane sulfonyl chlorides from trialkylaluminum and sulfuryl chloride |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3373192A (enrdf_load_stackoverflow) |
| NL (1) | NL254277A (enrdf_load_stackoverflow) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US667861A (en) * | 1900-08-25 | 1901-02-12 | Basle Chemical Works | Process of producing chlorids of aromatic sulfonic acids. |
| DE1050762B (de) * | 1957-06-18 | 1959-02-19 | Dr E H Karl Ziegler Dr | Verfahren zur Herstellung von Sulfinsaeuren |
| US3076044A (en) * | 1960-12-30 | 1963-01-29 | Armour & Co | Method of preparing long chain alkyl chlorides |
-
0
- NL NL254277D patent/NL254277A/xx unknown
-
1959
- 1959-08-20 US US834958A patent/US3373192A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US667861A (en) * | 1900-08-25 | 1901-02-12 | Basle Chemical Works | Process of producing chlorids of aromatic sulfonic acids. |
| DE1050762B (de) * | 1957-06-18 | 1959-02-19 | Dr E H Karl Ziegler Dr | Verfahren zur Herstellung von Sulfinsaeuren |
| US3076044A (en) * | 1960-12-30 | 1963-01-29 | Armour & Co | Method of preparing long chain alkyl chlorides |
Also Published As
| Publication number | Publication date |
|---|---|
| NL254277A (enrdf_load_stackoverflow) |
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