DE896345C - Process for the preparation of ªã-halo-oxycarboxamides from halogenated lactones - Google Patents
Process for the preparation of ªã-halo-oxycarboxamides from halogenated lactonesInfo
- Publication number
- DE896345C DE896345C DEP6019A DEP0006019A DE896345C DE 896345 C DE896345 C DE 896345C DE P6019 A DEP6019 A DE P6019A DE P0006019 A DEP0006019 A DE P0006019A DE 896345 C DE896345 C DE 896345C
- Authority
- DE
- Germany
- Prior art keywords
- oxycarboxamides
- halo
- lactones
- halogenated
- preparation
- 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
- 150000002596 lactones Chemical class 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- GILHWIBSHGKFQB-UHFFFAOYSA-N 2-(oxolan-2-yl)propanamide Chemical compound O1C(CCC1)C(C(=O)N)C GILHWIBSHGKFQB-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000000457 gamma-lactone group Chemical group 0.000 description 1
- -1 halogen lactone Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von @-Halogen-oxycarbonsäureamiden aus halogenierten Lactonen Die Erfindung betrifft ein Verfahren zur Herstellung von Halogen-oxycarbonsäureamiden aus halogenierten Lactonen.Process for the preparation of @ -halo-oxycarboxamides from halogenated Lactones The invention relates to a process for the preparation of halo-oxycarboxamides from halogenated lactones.
Es ist bekannt, daß man y- bzw. 8-Oxycarbonsäureamide aus den entsprechenden y- bzw. 8-Lactonen durch Behandeln mit Ammoniak oder Aminen erhalten kann. So beschreiben z. B. Schindler und Reichstein in Pharm. Acta Helv. 2o, 79 (I945) die Darstellung von Oxycarbonsäureamiden aus ihren Lactonen durch Kochen mit Aminen in Benzol unter Kohlendioxyd. Russel und Vander, Journ. Am. Chem. Soc. 69, 11 (I947), erhielten Oxycarbonsäureamide in 92"/oiger Ausbeute durch Umsetzung der Lactone mit flüssigem Ammoniak bei höheren Temperaturen.It is known that y- or 8-oxycarboxamides from the corresponding y- or 8-lactones can be obtained by treatment with ammonia or amines. So describe z. B. Schindler and Reichstein in Pharm. Acta Helv. 2o, 79 (1945) the presentation of oxycarboxamides from their lactones by boiling with amines in benzene under Carbon dioxide. Russel and Vander, Journ. At the. Chem. Soc. 69, 11 (1947) Oxycarboxamides in 92% yield by reacting the lactones with liquid Ammonia at higher temperatures.
Diese Methoden führen bei ihrer Anwendung zur Umsetzung eines @-Halogen-carbonsäure-y-lactons nicht zu dem entsprechenden Oxycarbonsäureamid, sondern z. B. im Falle des @-Chlor-önanthsäurey-lactons zum Tetrahydrofurylpropionsäureamid. Wie nachstehende Formelbilder zeigen, bildet sich hierbei wohl intermediär das gesuchte Oxysäureamid, wird aber sofort wieder unter Chlorwasserstoffabspaltung in das obengenannte Furanderivat übergeführt. Es wurde nun gefunden, daß sich @-halogenierte y-Lactone in @-Halogen-oxycarbonsäureamide überführen lassen, wenn man bei Temperaturen von o bis Zo° arbeitet und ein indifferentes Lösungsmittel verwendet, in welchem das Lacton gut löslich und das entsprechende Oxycarbonsäureamid schwer löslich ist, so daß das gebildete Produkt sogleich aus der Reaktion ausscheidet. Weiterhin darf das Lösungsmittel keine große Löslichkeit für Ammoniak besitzen, da sonst Halogenabspaltung und Furanringbildung eintritt.When applied to the implementation of a @ -halogenocarboxylic acid-y-lactone, these methods do not lead to the corresponding oxycarboxamide, but z. B. in the case of @ -Chlor-önanthsäurey-lactons to tetrahydrofurylpropionamide. As the following formulas show, the sought-after oxyamide is formed as an intermediate, but is immediately converted back into the abovementioned furan derivative with elimination of hydrogen chloride. It has now been found that -halogenated γ-lactones can be converted into -halo-oxycarboxamides if you work at temperatures from 0 to 0 ° and use an inert solvent in which the lactone is readily soluble and the corresponding oxycarboxamide is sparingly soluble is, so that the product formed is immediately eliminated from the reaction. Furthermore, the solvent must not have a high level of solubility for ammonia, since otherwise the splitting off of halogens and the formation of furan rings will occur.
Als geeignete Lösungsmittel erwiesen sich aromatische und halogenierte aliphatische Kohlenwasserstoffe. Unbrauchbar sind: Wasser, Alkohole sowie alle wasserhaltigen Lösungsmittel, da das in ihnen dissoziiert vorliegende Ammoniumhydroxyd quantitative HCl-Abspaltung bewirkt.Aromatic and halogenated solvents have proven to be suitable solvents aliphatic hydrocarbons. The following are unusable: water, alcohols and all water-containing ones Solvent, since the ammonium hydroxide present in them dissociates quantitative HCl splitting off causes.
Die Umsetzung erfolgt zweckmäßigerweise in der Art, daß der Lösung des Halogenlactons unter Eiskühlung ein Amin zugesetzt oder ein mäßiger Strom von trockenem Ammoniak durch die Lösung hindurchgeleitet wird, bis das Halogen-oxycarbonsäureamid ausfällt. Das kristallin ausfallende Amid läßt sich gut umkristallisieren und besitzt einen scharfen Schmelzpunkt. Halogen-oxycarbonsäureamide können zur Darstellung von Harzen dienen, die sich zum Teil zu Fäden und Filmen verformen lassen. Beispiel In 6o Gewichtsteilen Tetrachlorkohlenstoff, welcher über Calciumchlorid getrocknet worden ist, werden 2o Gewichtsteile @-Chlor-önanthsäure-y-lacton gelöst. Die Lösung wird mit Eiswasser gekühlt und ein mäßiger Strom von trockenem Ammoniakgas durchgeleitet. Nach 5 bis 7 Stunden besteht das Reaktionsgemisch aus einem kristallinen Brei, der sich gut absaugen läßt. Das Rohprodukt wird aus Chloroform umkristallisiert; das reine Erzeugnis fällt in weißen glänzenden Blättchen aus. Es schmilzt bei 8g°. Die Ausbeute beträgt z2,5 Gewichtsteile. Der Tetrachlorkohlenstoff enthält neben wenig Chlorlacton eine geringe Menge Tetrahydrofurylpropionsäureamid.The reaction is expediently carried out in such a way that the solution of the halogen lactone added an amine with ice cooling or a moderate stream of dry ammonia is passed through the solution until the halo-oxycarboxamide fails. The amide which precipitates out in crystalline form can be readily recrystallized and possesses a sharp melting point. Halo-oxycarboxamides can be used for the representation of resins, some of which can be shaped into threads and films. example In 60 parts by weight carbon tetrachloride, which is dried over calcium chloride 2o parts by weight of @ -chloro-oenanthic acid-y-lactone are dissolved. The solution is cooled with ice water and a moderate stream of dry ammonia gas is passed through it. After 5 to 7 hours, the reaction mixture consists of a crystalline slurry which can be suctioned off well. The crude product is recrystallized from chloroform; the pure product precipitates in white, shiny leaves. It melts at 8g °. the The yield is 2.5 parts by weight. The carbon tetrachloride contains next to little Chlorlactone a small amount of tetrahydrofurylpropionic acid amide.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP6019A DE896345C (en) | 1951-08-11 | 1951-08-11 | Process for the preparation of ªã-halo-oxycarboxamides from halogenated lactones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP6019A DE896345C (en) | 1951-08-11 | 1951-08-11 | Process for the preparation of ªã-halo-oxycarboxamides from halogenated lactones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE896345C true DE896345C (en) | 1953-11-12 |
Family
ID=7360365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEP6019A Expired DE896345C (en) | 1951-08-11 | 1951-08-11 | Process for the preparation of ªã-halo-oxycarboxamides from halogenated lactones |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE896345C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4992319A (en) * | 1988-05-18 | 1991-02-12 | Nichias Corporation | Activated carbon supporting honeycomb structure and process for fabricating the same |
-
1951
- 1951-08-11 DE DEP6019A patent/DE896345C/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4992319A (en) * | 1988-05-18 | 1991-02-12 | Nichias Corporation | Activated carbon supporting honeycomb structure and process for fabricating the same |
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