| Автор | Condon, F. E. |
| Автор | Waldman, Robert |
| Автор | Kundu, Nitya |
| Автор | Trivedi, J. P. |
| Дата выпуска | 1974 |
| Формат | application.pdf |
| Издатель | Taylor & Francis Group |
| Копирайт | Copyright Taylor and Francis Group, LLC |
| Название | 1,5-DIMETHYLTETRAZOLE |
| Тип | research-article |
| DOI | 10.1080/00304947409355086 |
| Electronic ISSN | 1945-5453 |
| Print ISSN | 0030-4948 |
| Журнал | Organic Preparations and Procedures International |
| Том | 6 |
| Первая страница | 135 |
| Последняя страница | 139 |
| Аффилиация | Condon, F. E.; Department of Chemistry, The City College of the City University of New York |
| Аффилиация | Waldman, Robert; Department of Chemistry, The City College of the City University of New York |
| Аффилиация | Kundu, Nitya; Department of Chemistry, The City College of the City University of New York |
| Аффилиация | Trivedi, J. P.; Department of Chemistry, The City College of the City University of New York |
| Выпуск | 3 |
| Библиографическая ссылка | German Patent 538,981. November 11, 1926. to Knoll A.-G. Chemische Fabriken; British Patent 280,529, November 10, 1926, to A. Boehringer |
| Библиографическая ссылка | Markgraf, J. M., Bachman, W. T. and Hollis, D. P. 1965. J. Org. Chem., 30: 3472 |
| Библиографическая ссылка | Bowers, D. M., Erlich, R. H., Policec, A. and Popov, A. I. 1971. J. Inorg. Nucl. Chem., 33: 81 |
| Библиографическая ссылка | Harvill, E. K., Herbst, R. M., Schreiner, E. C. and Roberts, C. W. 1950. J. Org. Chem., 15: 662 1,5-Dimethyltetrazole has also been prepared in 248 yield by reaction of hydrazoic acid with the imide chloride, MeC(Cl)=NMe, obtained by reaction of N-methylacetamide with phosphorus pentachloride |
| Библиографическая ссылка | In our hands, the use of sodium hydroxide often gave a liquid product containing much unreacted benzenesulfonyl chloride and difficult to crystallize and purify, while with pyridine no such difficulty was encountered |
| Библиографическая ссылка | The use of isolated sulfonic acid esters of oximes is described in the patent literature (ref. 1); but later workers (ref. 2,3) have carried out the reaction with the esters generated in situ, with fair to poor results |
| Библиографическая ссылка | Although the method is claimed to be widely applicable,<sup>1</sup> in our experience marked difference in the stabilities and reactivities of O-sulfonyl oximes make it necessary to work out optimum conditions individually in many cases |
| Библиографическая ссылка | Semon, W. L. 1932. “Organic Syntheses,” , Second Ed., Edited by: Gilman, H. and Blatt, A. H. Vol. 1, 318New York: Wiley. Coll., Acetoxime may also be prepared readily from acetone, 18% aqueous sodium hydroxide and commercially available hydroxylamine hydrochloride. An equivalent amount of a wet product (about 95% pure) may be used in this step. |
| Библиографическая ссылка | If the temperature is allowed to climb much above 30°, an uncontrollable exothermic decomposition sets in. |
| Библиографическая ссылка | Samples of acetoxime benzenesulfonate kept at room temperature have undergone vigorous exothermic decomposition. While the material may be kept under refrigeration, prolonged storage of large samples is inadvisable |
| Библиографическая ссылка | Oxley, P. and Short, W. F. J. Chem. Soc., 19481514 |
| Библиографическая ссылка | Wet methanol recovered from a previous run may be used but then it should be supplemented with 100-150 ml. of fresh methanol, and a correspondingly smaller amount of water should be used with the sodium azide, which may be added as a slurry with 100-150 ml. of water |
| Библиографическая ссылка | The use of larger amounts of material than described here is not recommended, because of difficulty in controlling the exothermic reaction |
| Библиографическая ссылка | Prior to distillation, the solution should be tested for acidity with pH paper. If acidic, it should be neutralized with sodium hydroxide to prevent the generation of explosive and toxic hydrazoic acid. The volume of distillate (1100-1200 ml.) assumes no vapor loss during the reaction and subsequent distillation. In any case, care should be taken not to overheat the residue in the flask, as some decomposition may occur. |
| Библиографическая ссылка | Evaporation to dryness may be done on a steam bath and is hastened by occasional thorough cooling of the residue and removal of crystallized solids by filtration with suction and their further drying in the air at ambient temperature. Alternatively, a rotary vacuum evaporator may be used. |
| Библиографическая ссылка | In the early extractions, there is a tendency for the pores of the Büchner funnel to become clogged through flash evaporation of the hot benzene. This can be prevented by pinching off the hose leading to the aspirator as soon as a vacuum has been established in the filtering flask. The filtration should be done in a hood with care to avoid inhaling vapors of the very toxic benzene. |
| Библиографическая ссылка | In production of 1,5-dimethyltetrazole on a large scale, the second benzene extract would be used to extract a second 360-g portion of solids (Portion B), and the third benzene extract would be used to extract Portion B a second time and then a third, fresh portion (Portion C), etc., so that each portion of solids is extracted five times, and only the last time with fresh benzene. The senior author has carried out these systematic extractions on kg-sized portions of solids in a 5-1. flask for the production of several kilograms of 1,5-dimethyltetrazole. The extraction might also be carried out with a Soxhlet extractor with an electrically heated solids chamber. Chloroform has been used for the extraction (ref. 2) but seems to have no advantage over the less expensive benzene. |
| Библиографическая ссылка | The recovered benzene may be reused, if desired. |
| Библиографическая ссылка | While there have been no reports of explosions from heating 1,5-dimethyltetrazole, suitable precautions should be taken against damage in the event of an explosion at this stage, as benzenesulfonyl azide and other explosive azo compounds are likely contaminants. |
