DE545850C - Process for the preparation of tetrazoles - Google Patents
Process for the preparation of tetrazolesInfo
- Publication number
- DE545850C DE545850C DEB130640D DEB0130640D DE545850C DE 545850 C DE545850 C DE 545850C DE B130640 D DEB130640 D DE B130640D DE B0130640 D DEB0130640 D DE B0130640D DE 545850 C DE545850 C DE 545850C
- Authority
- DE
- Germany
- Prior art keywords
- acid
- chloroform
- pyridine
- tetrazoles
- azides
- 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
Links
- 238000000034 method Methods 0.000 title claims description 9
- 150000003536 tetrazoles Chemical class 0.000 title claims description 7
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- -1 pyridine Chemical class 0.000 claims description 10
- 150000001408 amides Chemical class 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001540 azides Chemical class 0.000 claims description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- JUINSXZKUKVTMD-UHFFFAOYSA-N hydrogen azide Chemical compound N=[N+]=[N-] JUINSXZKUKVTMD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 150000001805 chlorine compounds Chemical class 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 6
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 3
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- CWRVKFFCRWGWCS-UHFFFAOYSA-N Pentrazole Chemical compound C1CCCCC2=NN=NN21 CWRVKFFCRWGWCS-UHFFFAOYSA-N 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Darstellung von Tetrazolen Nach dem Verfahren des Patents 543 025, Zusatz zum Patent 538 981, gelangt man dadurch zu Tetrazolen, daß man Säurechloride auf monosubstituierte Säureamide einwirken läßt und das als Zwischenprodukt auftretende Amidchlorid zweckmäßig im rohen Zustand mit 'Stickstoffwasserstoffsäure oder Aziden zur Umsetzung bringt, gegebenenfalls unter Mitverwendung indifferenter Lösungsmittel, wie Chloroform.Method for the preparation of tetrazoles According to the method of the patent 543 025, addendum to patent 538 981, tetrazoles are obtained by using acid chlorides can act on monosubstituted acid amides and the occurring as an intermediate Amide chloride conveniently in the crude state with hydrazoic acid or azides brings to implementation, if necessary with the use of inert solvents, like chloroform.
Wie nun weiterhin gefunden wurde, gelangt man glatter und in noch besseren Ausbeuten zu Tetrazolen von monosubstituierten Säureamiden ausgehend, wenn man. auf diese Säureamide Säurechloride, wie Phosphoroxychlorid oder Benzolsulfochlorid, bei Gegenwart organischer Basen, wie Pyridin, gegebenenfalls bei Anwesenheit indifferenter organischer Lösungsmittel, wie Chloroform, einwirken läßt und das Reaktionsgemisch sodann mit Stickstoffwasserstoffsäure oder Aziden behandelt. Vermutlich handelt es sich dabei um Derivate der Enolform der Säureamide, die in Reaktion treten, da man, wie im Patent 538 98i gezeigt ist, auch ausgehend von Oximestern zu Tetrazolen gelangt, wenn man die Oximester in Gegenwart von Stickstoffwasserstoffsäure oder Aziden umlagert oder die Umlagerungsprodukte nachträglich mit der Säure oder ihren Salzen behandelt. Stickstoffwasserstoftsäure bzw. Azide werden dabei zweckmäßig in Mengen von i Mol. oder darüber, jedoch nicht über 2 Mol., verwendet.As has now been further found, one arrives smoother and in still better yields to tetrazoles starting from monosubstituted acid amides, if man on these acid amides acid chlorides, such as phosphorus oxychloride or benzenesulfochloride, in the presence of organic bases, such as pyridine, optionally in the presence of more indifferent ones organic solvent, such as chloroform, is allowed to act and the reaction mixture then treated with hydrazoic acid or azides. Presumably acts these are derivatives of the enol form of the acid amides that react because as shown in patent 538 98i, starting from oxime esters to tetrazoles obtained when the oxime ester in the presence of hydrazoic acid or Azides rearranged or the rearrangement products subsequently with the acid or its Salts treated. Hydrazoic acid or azides are useful here in amounts of 1 mole. Or more, but not more than 2 moles. Used.
Beispiele i. 73 g Methylacetamid werden in einer Mischung von ioo g trockenem Pyridin und Soo ccm Chloroform gelöst, worauf man unter Kühlung 176 g Benzolsulfochlorid zutropfen läßt. Das Reaktionsgemisch wird unter guter Kühlung i Stunde lang gerührt, wobei für Ausschluß von Feuchtigkeit Sorge zu tragen ist. Dann versetzt man unter kräftigem Rühren mit 65 g fein gepulvertem Natriumazid, oder man trägt die Chloroformlösung des Lactimesters unter kräftigem Rühren in eine gesättigte wäßrige Natriumazidlösung ein. Man erhält i, 5-Dimethyl-i, 2, 3, 4-tetrazol vom Schmelzpunkt 7o bis 7i°. Ausbeute 6i% der Theorie.Examples i. 73 g of methylacetamide are in a mixture of ioo g of dry pyridine and 50 cc of chloroform are dissolved, whereupon 176 g of benzenesulfonyl chloride can be added dropwise. The reaction mixture is cooled well Stirred for i hour, care being taken to exclude moisture. Then, while stirring vigorously, 65 g of finely powdered sodium azide are added, or the chloroform solution of the lactim ester is carried into a with vigorous stirring saturated aqueous sodium azide solution. I, 5-Dimethyl-i, 2, 3, 4-tetrazole is obtained from the melting point of 70 to 71 °. Yield 61% of theory.
2. Eine Lösung von 68 g Acetanilid in 5o g trockenem Pyridin und 30o ccm trockenem Chloroform werden bei unter o° liegender Temperatur allmählich mit 92,g Benzolsulfochlorid versetzt. Man läßt unter guter Kühlung i Stunde stehen, dann versetzt man mit 35 g gepulvertem Natriumazid oder läßt die Chloroformlösung in eine wäßrige Lösung von 33 g Natriurnazid einfließen. Nach mehrstündiger Einwirkung wird mit Wasser versetzt, neutralisiert und dieChloroformlösung abgeschieden. Der Rückstand :von'dieser wird in wäßrig alkoholischer Lösung mit Alkali gekocht zwecks Verseifung vo'ri nicht umgesetztem Säureamid. Man erhält i-Phenyl-5-methvli, 2, 3, 4-tetrazol vom Schmelzpunkt 98 bis 99° in einer Ausbeute von 5o bis 6o °(" der Theorie.2. A solution of 68 g acetanilide in 5o g dry pyridine and 30o ccm of dry chloroform are gradually absorbed at a temperature below 0 ° 92 g of benzenesulfonyl chloride were added. It is left to stand under good cooling for an hour, 35 g of powdered sodium azide are then added or the chloroform solution is left pour into an aqueous solution of 33 g of sodium azide. After several hours of exposure is mixed with water, neutralized and the chloroform solution deposited. The residue: von'dieser in aqueous alcoholic solution with Boiled alkali for the saponification of unreacted acid amide. I-phenyl-5-methane is obtained, 2, 3, 4-tetrazole with a melting point of 98 to 99 ° in a yield of 5o to 6o ° (" the theory.
3. 11,3 g e-Leucinlactam werden mit 3 Mol. Pyridin und i Mol. Phosphoroxychlorid unter Kühlung in Choroform behandelt, dann gibt man ill2 Mol. Natriumazid zu. Ausbeute 4. 11,3 g e-Leucinlactam werden mit i Mol. Py ridin und i Mol. Benzolsulfochlorid unter Kühlung in Chloroform behandelt. Nach einiger Zeit gibt man i% Mol. Natriumazid zu und erwärmt bis 5o°. Ausbeute 6o °1".3. 11.3 g of e-leucine lactam are treated with 3 mol. Pyridine and 1 mol. Phosphorus oxychloride with cooling in choroform, then ill2 mol. Sodium azide are added. Yield 4. 11.3 g of e-leucine lactam are treated with 1 mole of pyridine and 1 mole of benzenesulfonyl chloride with cooling in chloroform. After a while, 1% mol. Of sodium azide is added and the mixture is heated to 50 °. Yield 60 ° 1 ".
5. 45,2g e-Leucinlactam werden mit i Mol. Pyridin und i Mol. Benzolsulfochlorid verestert. Das Reaktionsgemisch wird mit einer gesättigten wäßrigen Lösung von i'J; Mol, Natriumazid umgesetzt. Ausbeute 75 °j" an a, ß-Cyclopentamethylentetrazol.5. 45.2 g of e-leucine lactam are treated with 1 mole of pyridine and 1 mole of benzenesulfonyl chloride esterified. The reaction mixture is treated with a saturated aqueous solution of i'J; Mol, sodium azide reacted. Yield 75 ° j "of α, β-cyclopentamethylene tetrazole.
Das vorliegende Verfahren gestattet wie dasjenige des Hauptpatents 543025 die als Nebenprodukte im Verfahren des Patents 538 981 sowie die beim Verfahren der Patentschrift 439 041 abfallenden Säureamide wieder zur Tetrazoldarstellung zu verwenden. Außerdem bietet es gegenüber dem Veffahren des Hauptpatents den Vorteil höherer Ausbeuten.The present process, like that of the main patent 543025, allows the acid amides which fall off as by-products in the process of patent 538 981 and the acid amides in the process of patent specification 439 041 to be used again for the preparation of tetrazole. In addition, it offers the advantage of higher yields over the process of the main patent.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB130640D DE545850C (en) | 1927-03-31 | 1927-03-31 | Process for the preparation of tetrazoles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB130640D DE545850C (en) | 1927-03-31 | 1927-03-31 | Process for the preparation of tetrazoles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE545850C true DE545850C (en) | 1932-03-05 |
Family
ID=6997667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB130640D Expired DE545850C (en) | 1927-03-31 | 1927-03-31 | Process for the preparation of tetrazoles |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE545850C (en) |
-
1927
- 1927-03-31 DE DEB130640D patent/DE545850C/en not_active Expired
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE545850C (en) | Process for the preparation of tetrazoles | |
| DE540409C (en) | Process for the preparation of tetrazoles | |
| DE2520131B2 (en) | 1,1-disubstituted octahydro-indolo [2r3-a] quinolizines and processes for their preparation | |
| DE904534C (en) | Process for the preparation of nicotinic acid ester nitrates | |
| DE522064C (en) | Process for the preparation of Monoalkoxyaminobenzoesaeurealkaminestern | |
| DE538981C (en) | Process for the preparation of tetrazoles | |
| DE550620C (en) | Process for the preparation of therapeutically valuable organic mercury compounds | |
| DE965325C (en) | Process for the preparation of streptomycin isonicotinic acid hydrazone and its salts | |
| DE800413C (en) | Process for the production of neutral solutions of polyalkylxanthines | |
| AT217048B (en) | Process for the preparation of new theophylline derivatives substituted in the 7-position | |
| AT126139B (en) | Process for the preparation of basic nitro derivatives of 9-aminoacridine. | |
| DE2107866C3 (en) | Thiamphenicol derivatives, processes for their preparation and anabolic agent | |
| DE543025C (en) | Process for the preparation of tetrazoles | |
| DE713079C (en) | Process for the preparation of clusters of 4-aminobenzenesulfonamides | |
| DE928530C (en) | Process for the preparation of p-aminosalicylates from antihistamine bases | |
| DE1803911C3 (en) | Process for the preparation of 7-chloro-2-methylamino-5-phenyl-3H-1,4benzodiazepine-4-oxide | |
| DE883435C (en) | Process for the preparation of dioxyacetone compounds | |
| DE611692C (en) | Process for the preparation of cyclically disubstituted tetrazoles | |
| DE956226C (en) | Process for the production of biologically active compounds of <<desacetylthiolutin>> | |
| AT133364B (en) | Process for the preparation of tetrazoles. | |
| DE844300C (en) | Process for the preparation of 5-nitro-uracil-carboxylic acid (4) or derivatives thereof substituted on the nitrogen atom | |
| DE915812C (en) | Process for the production of xanthanes or thioxanthanes | |
| DE2550430A1 (en) | PROCESS FOR THE PREPARATION OF N-METHYL-N-HYDROXIAETHYLGUANIDINE-PHOSPHORIC ACID ESTER | |
| DE481599C (en) | Process for the production of solid, permanent, water-soluble coagulations of dyes from the vat | |
| AT143314B (en) | Process for the preparation of tetrazoles. |