DE162395C - - Google Patents
Info
- Publication number
- DE162395C DE162395C DENDAT162395D DE162395DA DE162395C DE 162395 C DE162395 C DE 162395C DE NDAT162395 D DENDAT162395 D DE NDAT162395D DE 162395D A DE162395D A DE 162395DA DE 162395 C DE162395 C DE 162395C
- Authority
- DE
- Germany
- Prior art keywords
- formaldehyde
- acetone
- extracted
- acid
- added
- 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.)
- Active
Links
- -1 aliphatic acid amides Chemical class 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- SLARRVWTFDSJRB-UHFFFAOYSA-N [NH-]CO Chemical class [NH-]CO SLARRVWTFDSJRB-UHFFFAOYSA-N 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000006011 modification reaction Methods 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BDKZHNJTLHOSDW-UHFFFAOYSA-N [Na].CC(O)=O Chemical compound [Na].CC(O)=O BDKZHNJTLHOSDW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VDGDOWDNOPBCRE-UHFFFAOYSA-N 2,2,2-trichloro-N-(hydroxymethyl)acetamide Chemical compound OCNC(=O)C(Cl)(Cl)Cl VDGDOWDNOPBCRE-UHFFFAOYSA-N 0.000 description 1
- UPQQXPKAYZYUKO-UHFFFAOYSA-N 2,2,2-trichloroacetamide Chemical compound OC(=N)C(Cl)(Cl)Cl UPQQXPKAYZYUKO-UHFFFAOYSA-N 0.000 description 1
- SJYLPGUDCXMZQO-UHFFFAOYSA-N 2-bromo-N-(hydroxymethyl)acetamide Chemical compound OCNC(=O)CBr SJYLPGUDCXMZQO-UHFFFAOYSA-N 0.000 description 1
- JUIKUQOUMZUFQT-UHFFFAOYSA-N 2-bromoacetamide Chemical compound NC(=O)CBr JUIKUQOUMZUFQT-UHFFFAOYSA-N 0.000 description 1
- AUHYZQCEIVEMFH-UHFFFAOYSA-N 2-bromopropanamide Chemical compound CC(Br)C(N)=O AUHYZQCEIVEMFH-UHFFFAOYSA-N 0.000 description 1
- ATGFZSOBDDZEEX-UHFFFAOYSA-N 2-chloro-3-hydroxypropanamide Chemical compound NC(=O)C(Cl)CO ATGFZSOBDDZEEX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N Chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- PGLTVOMIXTUURA-UHFFFAOYSA-N Iodoacetamide Chemical compound NC(=O)CI PGLTVOMIXTUURA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
M 162395 KLASSE 12 o. M 162395 CLASS 12 o.
Das durch Patent 158088 geschützte Verfahren gestattet die Darstellung der Methylolderivate aromatischer Säureamide durch Kondensation aromatischer Säureamide mit Formaldehyd in Gegenwart von Säuren.The process protected by patent 158088 allows the preparation of methylol derivatives aromatic acid amides by condensation of aromatic acid amides with formaldehyde in the presence of acids.
Es wurde nun gefunden, daß in gleicher Weise analoge Verbindungen auch aus halogensubstituierten, aliphatischen Säureamiden gewonnen werden können, während es nichtIt has now been found that analogous compounds also consist of halogen-substituted, aliphatic acid amides can be obtained while it is not
ίο gelingt, solche Methylolderivate aus einfachen aliphatischen Säureamiden, wie Acetamid, zu isolieren.ίο succeeds in making such methylol derivatives from simple aliphatic acid amides, such as acetamide, to isolate.
Die erhältlichen neuen Verbindungen sollen als Ausgangsprodukte zur Darstellung neuer Produkte für pharmakologische und photographische Zwecke verwendet werden.The available new compounds are intended as starting products for the representation of new Products used for pharmacological and photographic purposes.
Beispiel I: Zu 2 T. Monochloracetamid fügt man 2 T. Formaldehyd von 40 Prozent und 0,5 T. konzentrierte Salzsäure und digeriert etwa 2 Minuten auf dem Wasserbad, bis Lösung erfolgt; dann läßt man erkalten, fügt nach etwa 4 Stunden Natriumacetat hinzu und dunstet die Masse im Vakuum ein, wobei ein halbfester sirupöser Rückstand hinterbleibt, den man mit Aceton extrahiert. Beim Verdunsten des Lösungsmittels erhält man dann ein dickflüssiges Öl, das allmählich zum Methylolchloracetamid erstarrt. Es kristallisiert aus Aceton in prismatischen Nadeln oder Blättchen, die bei 97 bis 990 schmelzen und beim Erhitzen Formaldehyd abspalten.Example I: 2 parts of 40 percent formaldehyde and 0.5 parts of concentrated hydrochloric acid are added to 2 parts of monochloroacetamide and the mixture is digested for about 2 minutes on a water bath until it dissolves; then allowed to cool, sodium acetate is added after about 4 hours and the mass evaporates in vacuo, leaving a semi-solid syrupy residue which is extracted with acetone. When the solvent evaporates, a thick oil is obtained that gradually solidifies to form methylolchloroacetamide. It crystallizes from acetone in prismatic needles or leaflets, which melt at 97 to 99 0 and split off formaldehyde when heated.
Beispiel II: 2 T. Trichloracetamid und 6 T. Formaldehyd werden mit verdünnter Schwefelsäure versetzt und auf dem Wasserbad IY2 Stunden erwärmt. Die dann filtrierte Lösung wird mit Äther extrahiert, die Ätherlösung mit Wasser gewaschen und verdunstet. Der ölige Rückstand erstarrt allmählich zum Methyloltrichloracetamid, das aus Benzol in bei 92 bis 940 schmelzenden Nädelchen kristallisiert und beim Erhitzen Formaldehyd abspaltet.Example II: 2 parts of trichloroacetamide and 6 parts of formaldehyde are mixed with dilute sulfuric acid and heated on the water bath IY for 2 hours. The then filtered solution is extracted with ether, the ether solution is washed with water and evaporated. The oily residue gradually solidifies to Methyloltrichloracetamid which crystallizes from benzene in at 92 to 94 0 needles melting and splits off formaldehyde upon heating.
Beispiel III: Man erwärmt ig Monobromacetamid, 1,3 g Formaldehyd von 41 Prozent und 0,5 g konzentrierte Salzsäure etwa ι Minute auf dem Wasserbad, wobei Lösung erfolgt, und fügt nach 1J4 Stunde essigsaures Natrium hinzu, dann bringt man die Masse in den Exsikkator, wobei sie zu einem Sirup eindickt, den man mit Aceton extrahiert. Die Lösung erstarrt nach dem Verdunsten des Acetons nach einigen Tagen allmählich zum MethylolbromacetamidExample III: Monobromoacetamide, 1.3 g of 41 percent formaldehyde and 0.5 g of concentrated hydrochloric acid are heated on a water bath for about 1 minute, during which process dissolution occurs, and sodium acetic acid is added after 1 and 4 hours, then the mass is added into the desiccator, thickening to a syrup that is extracted with acetone. After the acetone has evaporated, the solution gradually solidifies after a few days to form methylol bromoacetamide
CH2 Br-CO- NH- CH2 OH,CH 2 Br-CO- NH- CH 2 OH,
welches sich aus Benzol in verfilzten Kristallen abscheidet, die bei 94 bis 950 schmelzen und beim Erhitzen Formaldehyd abspalten.which separates from benzene in matted crystals, which melt at 94 to 95 0 and split off formaldehyde when heated.
Beispiel IV: Man fügt 0,2 g konzentrierte Salzsäure zu einer Suspension von 1 g Monojodacetamid in 0,5 g Formaldehyd von 41 Prozent, wobei nach einiger Zeit ohne äußere Wärmezufuhr Lösung erfolgt, nach etwaExample IV: 0.2 g of concentrated hydrochloric acid is added to a suspension of 1 g of monoiodoacetamide in 0.5 g formaldehyde of 41 percent, with after some time without external Heat solution takes place after about
1J2 Stunde versetzt man dann mit essigsaurem Natrium, filtriert event, eine ganz geringe Ausscheidung ab und dunstet die Flüssigkeit im Exsikkator zur Trockne ein. Extrahiert man dann mit 'Aceton, so geht Methyloljodacetamid CK2 J-CO- NH- CK2 OK in Lösung, welches aus Wasser kristallisiert und bei 1280 schmilzt. Beim Erhitzen stößt die Verbindung Joddämpfe aus und entbindet Formaldehyd. Acetic acid sodium is then added for 1 and 2 hours, if necessary, a very small amount of precipitate is filtered off and the liquid evaporates to dryness in the desiccator. Then it is extracted with 'acetone so goes Methyloljodacetamid CK 2 J-CO- NH- CK 2 OK in solution which crystallized from water and melts at 128 0th When heated, the compound emits iodine vapors and releases formaldehyde.
Beispiel V: Man erwärmt eine Mischung von 3 g a-Brompropionsäureamid, 1,5 g Formaldehyd von 41,18 Prozent, 1!/2 g Wasser und 11IiS konzentrierte Salzsäure ab und zu auf dem schwach siedenden Wasserbad, wobei man in etwa 2 Minuten eine klare Lösung erhält. Diese wird nach 1J2 Stunde mit verdünntem essigsauren Natron versetzt, um die Mineralsäure unschädlich zu machen, und über Nacht stehen gelassen. Während dieser Zeit scheiden sich aus der ursprünglich klaren Flüssigkeit 0,2g Kristalle ab, die man entfernt, das Filtrat wird dann im Exsikkator eingedunstet, wobei eine mit Kristallen durchsetzte, sirupöse Reaktionsmasse hinterbleibt, die bei gewöhnlicher Temperatur mit Aceton extrahiert wird. Beim Verdunsten des Lösungsmittels erhält man wieder einen halbfesten Rückstand, aus dem man das kristallisierte Methylol-a-brompropionsäureamid abfiltriert. Die sirupöse Mutterlauge zieht man nun noch mit Äther aus, beim Verdunsten derselben hinterbleibt dann ein Öl, welches noch weitere Mengen des kristallisierten Methylol-ct-brompropionsäureamids abscheidet. Das Methylol-a-brompropionsäureamidExample V: A mixture of 3 g of α-bromopropionic acid amide, 1.5 g of 41.18 percent formaldehyde, 1 ! / 2 g of water and 11 liters of concentrated hydrochloric acid from time to time on the low-boiling water bath, a clear solution being obtained in about 2 minutes. This is after 1 year 2 hours mixed with dilute acetic acid soda, render harmless the mineral acid and left to stand overnight. During this time 0.2 g of crystals separate from the originally clear liquid, which are removed, the filtrate is then evaporated in the desiccator, leaving a syrupy reaction mass interspersed with crystals, which is extracted with acetone at ordinary temperature. When the solvent evaporates, a semisolid residue is again obtained, from which the crystallized methylol-a-bromopropionic acid amide is filtered off. The syrupy mother liquor is now extracted with ether; when it evaporates, an oil then remains, which separates further amounts of the crystallized methylol-ct-bromopropionic acid amide. The methylol-a-bromopropionic acid amide
CH5-CHBr'CO-NK-CK2OKCH 5 -CHBr'CO-NK-CK 2 OK
kristallisiert aus Benzol in prismatischen Nadeln vom Schmelzpunkt 920, beim Erhitzen spaltet die Verbindung Formaldehyd ab.crystallizes from benzene in prismatic needles with a melting point of 92 ° ; on heating the compound splits off formaldehyde.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE162395C true DE162395C (en) |
Family
ID=428194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT162395D Active DE162395C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE162395C (en) |
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0
- DE DENDAT162395D patent/DE162395C/de active Active
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