US2525410A - Stabilization of tetrahydrofuran - Google Patents
Stabilization of tetrahydrofuran Download PDFInfo
- Publication number
- US2525410A US2525410A US2525410DA US2525410A US 2525410 A US2525410 A US 2525410A US 2525410D A US2525410D A US 2525410DA US 2525410 A US2525410 A US 2525410A
- Authority
- US
- United States
- Prior art keywords
- tetrahydrofuran
- peroxide
- hydroquinone
- stabilization
- concentrations
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims description 94
- 238000011105 stabilization Methods 0.000 title description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N benzohydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 34
- 230000000087 stabilizing Effects 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000005755 formation reaction Methods 0.000 description 8
- NLKNQRATVPKPDG-UHFFFAOYSA-M Potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-Benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- -1 heterocyclic organic compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- SEGHOGJPPSQKTH-UHFFFAOYSA-N C1(O)=CC=C(O)C=C1.O1CCCC1 Chemical compound C1(O)=CC=C(O)C=C1.O1CCCC1 SEGHOGJPPSQKTH-UHFFFAOYSA-N 0.000 description 2
- 235000007575 Calluna vulgaris Nutrition 0.000 description 2
- 241000353097 Molva molva Species 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L Sodium thiosulphate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000020639 clam Nutrition 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
Definitions
- This invention relates to the stabilization of heterocyclic organic compounds and in particular it relates to the stabilization of tetrahydrofuran.
- Tetrahydrofuran is a colorless liquid which is a potentially important and valuable intermediate for the preparation of a wide variety of organic compounds.
- An obstacle to its extensive use is the fact that it forms peroxides during storage.
- freshly distilled tetrahydrofuran sometimes contains small concentrations of peroxide, in the order of a few hundredths of one per cent, which are relatively harmless, upon standing for a comparatively short period, the peroxide concentration rapidly increases to the point where the material becomes unsafe to handle.
- Peroxide formation in tetrahydrofuran not only introduces an undesirable impurity but also results in a hazardous condition since'the peroxide formed may decompose with explosive violence when relatively high concentrations are present part cularly when the material is distilled or heated. No method has heretofore been available for stabilizing tetrahydrofuran.
- Tetrahydrofuran stabilized in accordance with my invention may be stored over relatively long periods without the development of hazardous concentrations of peroxide.
- hydroquinone may be utilized in the practice of my invention although I prefer to utilize concentrations within the range 0.05 to 1.0% by weight. Concentrations above 1.0% may be used successfully but in general amounts greater than 1.0% are unncessary for satisfactory results. Less than 0.05% of hydroquinone may be utilized but for consistently satisfactory results concentrations of at least Example A glass-stoppered clear glass bottle was half filled with freshly distilled anhydrous tetrahydrofuran containing 0.1 hydroquinone. The bottle containing the tetrahydrofuran and hydroquinone was stored in diifused light and an analysis of the peroxide content was made from time to time. The analysis for peroxide content was made by pipetting a 10 cc.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Oct. 10, 1950 UNITED STATES PATENT OFFICE STABILIZATION 0F TETRAHYDROFURAN Wilbie S. Hinegardner, Niagara Falls, N. Y., as-
signor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application December 19, 1946,
Serial No. 717,315
2 Claims.
This invention relates to the stabilization of heterocyclic organic compounds and in particular it relates to the stabilization of tetrahydrofuran.
Tetrahydrofuran is a colorless liquid which is a potentially important and valuable intermediate for the preparation of a wide variety of organic compounds. An obstacle to its extensive use is the fact that it forms peroxides during storage. Although freshly distilled tetrahydrofuran sometimes contains small concentrations of peroxide, in the order of a few hundredths of one per cent, which are relatively harmless, upon standing for a comparatively short period, the peroxide concentration rapidly increases to the point where the material becomes unsafe to handle. Peroxide formation in tetrahydrofuran not only introduces an undesirable impurity but also results in a hazardous condition since'the peroxide formed may decompose with explosive violence when relatively high concentrations are present part cularly when the material is distilled or heated. No method has heretofore been available for stabilizing tetrahydrofuran.
It is an object of this invention to provide a novel method for the stabilization of tetrahydrofuran. Another object is to inhibit peroxide formation in tetrahydrofuran. A further object is to provide a new stabilizer for tetrahydrofuran. An additional object is to provide a relatively stable tetrahydrofuran composition. These and other objects will be apparent from the following description of my invention.
The above objects are attained in accordance with my invention by incorporating into tetrahydrofuran hydroquinone.
I have discovered that when small amounts of hydroquinone are incorporated into tetrahydrofuran peroxide formation is substantially inh bited and a relatively stable composition results. Tetrahydrofuran stabilized in accordance with my invention may be stored over relatively long periods without the development of hazardous concentrations of peroxide.
Various concentrations of hydroquinone may be utilized in the practice of my invention although I prefer to utilize concentrations within the range 0.05 to 1.0% by weight. Concentrations above 1.0% may be used successfully but in general amounts greater than 1.0% are unncessary for satisfactory results. Less than 0.05% of hydroquinone may be utilized but for consistently satisfactory results concentrations of at least Example A glass-stoppered clear glass bottle was half filled with freshly distilled anhydrous tetrahydrofuran containing 0.1 hydroquinone. The bottle containing the tetrahydrofuran and hydroquinone was stored in diifused light and an analysis of the peroxide content was made from time to time. The analysis for peroxide content was made by pipetting a 10 cc. sample of tetrahydrofuran into an excess of potassium iodide in dilute sulfuric acid solution and allowing the sample to stand in the dark during 10 minutes. The liberated iodine was then determined by titration with a standard sodium thiosulfate solution. A second sample containing 0.05% hyroquinone was prepared and tested in the same manner. The results are shown in tabular form below:
00. 0.1 N Thiosulfate/lO cc. Sample Time in Days Control (No 0.05% 0.1%
Hydro- Hydro- Hydroquinone) quinone quinone 1 One cc. of this solution/l0 cc. sample of tetrahydrofuran is equivalent to approximately 0.05% peroxide when it is assumed that the peroxide contains one mole of tetrahydrofuran.
The foregoing data conclusively demonstrate the inhibiting effect of hydroquinone on peroxide formation in tetrahydrofuran. No appreciable tively long periods or shipped long distances without appreciable deterioration but also the 7 3 hazard inherent in the presence of peroxides in UNITED STATES PATENTS the tetrahydrofuran is held to a minimum. Number Name Date I clam r 2,114,832 Evans Apr. 19,1938 1. The method for stabilizing tetrahydrofuran 2,489,260 Bordner Nov. 29, 1949 which comprises incorporating therein 0.05 to 5 1.0% of hydroquinone. OREIGN PATENTS 2. A stable tetrahydrofuran composition com- Number Country t prising tetrahydrofuran ha ling inco p r 532,158 Great Britain Jan. 17, 1941 therein 0.05 to 1.0% of hydroqulnone. 10 OTHER REFERENCES WILBIE S. HINEGARDNER. Gilman: Organic Chem. An Advanced Treatise, vol. I, 2nd edition, pages 656 and 657. John REFERENCES CITED Wiley and Sons, New York.
The following references are of record in the Daubert: Amer Pharm' ASS-y pages file of this patent:
Chem. Abstracts, volume 39, page 2024.
Claims (1)
1. THE METHOD FOR STABILIZING TETRAHYDROFURAN WHICH COMPRISES INCORPORATING THEREIN 0.05 TO 1.0% OF HYDROQUINONE.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2525410A true US2525410A (en) | 1950-10-10 |
Family
ID=3437508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2525410D Expired - Lifetime US2525410A (en) | Stabilization of tetrahydrofuran |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2525410A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2617811A (en) * | 1952-11-11 | Inhibiting peroxidation of tetra | ||
| DE948506C (en) * | 1954-01-13 | 1956-09-06 | Hoechst Ag | Stabilizer for tetrahydrofuran |
| US2914540A (en) * | 1957-07-05 | 1959-11-24 | Hercules Powder Co Ltd | Stabilization of monomeric 3, 3-bis(chloromethyl)-oxetane |
| CN104557803A (en) * | 2014-12-31 | 2015-04-29 | 宏业生化股份有限公司 | Stabilizer prolonging furfuryl alcohol storing time and application of stabilizer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2114832A (en) * | 1936-08-17 | 1938-04-19 | Shell Dev | Stabilization of aliphatic mixed ethers |
| GB532158A (en) * | 1938-09-16 | 1941-01-17 | Melle Usines Sa | Improvements in or relating to the polymerisation of di-olefines |
| US2489260A (en) * | 1946-04-20 | 1949-11-29 | Du Pont | Stabilization of tetrahydrofuran |
-
0
- US US2525410D patent/US2525410A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2114832A (en) * | 1936-08-17 | 1938-04-19 | Shell Dev | Stabilization of aliphatic mixed ethers |
| GB532158A (en) * | 1938-09-16 | 1941-01-17 | Melle Usines Sa | Improvements in or relating to the polymerisation of di-olefines |
| US2489260A (en) * | 1946-04-20 | 1949-11-29 | Du Pont | Stabilization of tetrahydrofuran |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2617811A (en) * | 1952-11-11 | Inhibiting peroxidation of tetra | ||
| DE948506C (en) * | 1954-01-13 | 1956-09-06 | Hoechst Ag | Stabilizer for tetrahydrofuran |
| US2914540A (en) * | 1957-07-05 | 1959-11-24 | Hercules Powder Co Ltd | Stabilization of monomeric 3, 3-bis(chloromethyl)-oxetane |
| CN104557803A (en) * | 2014-12-31 | 2015-04-29 | 宏业生化股份有限公司 | Stabilizer prolonging furfuryl alcohol storing time and application of stabilizer |
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