DE297847C - - Google Patents
Info
- Publication number
- DE297847C DE297847C DENDAT297847D DE297847DA DE297847C DE 297847 C DE297847 C DE 297847C DE NDAT297847 D DENDAT297847 D DE NDAT297847D DE 297847D A DE297847D A DE 297847DA DE 297847 C DE297847 C DE 297847C
- Authority
- DE
- Germany
- Prior art keywords
- formaldehyde
- parts
- formic acid
- base
- ether
- 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
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 235000019253 formic acid Nutrition 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- -1 heterocyclic amino alcohols Chemical group 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N Diphenhydramine Chemical class C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001184 potassium carbonate Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- ASZLNPRMVCGYCI-UHFFFAOYSA-N 1$l^{2}-azolidine Chemical group C1CC[N]C1 ASZLNPRMVCGYCI-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000001476 alcoholic Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/08—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
KLASSE i2q. GRUPPECLASS i2q. GROUP
FARBENFABRIKEN vorm. FRIEDR. BAYER & CO. in LEVERKUSEN β. COLN a. Rh.FARBENFABRIKEN vorm. FRIEDR. BAYER & CO. in LEVERKUSEN β. COLN a. Rh.
Verfahren zur Darstellung von N-Methylderivaten sekundärer aliphatischer und heterocyklischer Aminoalkohole.Process for the preparation of N-methyl derivatives of secondary aliphatic and heterocyclic amino alcohols.
Patentiert im Deutschen Reiche vom 5. November 1915 ab.Patented in the German Empire on November 5, 1915.
Aus der Patentschrift 287802, Kl.. 12p, ist ein Verfahren zur Darstellung von N-Methylderivaten organischer Basen bekannt, das darin besteht, daß man primäre oder sekundäre Amine mit Formaldehyd behandelt, wobei, soweit die betreffenden Amine nicht gleichzeitig einen leicht oxydierbaren Substituenten, wie die Alkoholgruppe, enthalten, in Gegenwart oxydierbarer organischer Verbindungen, mit Ausnahme von Ameisensäure und Formaldehyd, gearbeitet wird. Dieses Verfahren ist dadurch gekennzeichnet, daß dabei Oxydation der alkoholischen — CH(OH)-Gruppe eintritt.From the patent specification 287802, Kl .. 12p, is a process for the preparation of N-methyl derivatives of organic bases known that consists in treating primary or secondary amines with formaldehyde, whereby, if the amines in question do not have an easily oxidizable substituent at the same time, like the alcohol group, contain, in the presence of oxidizable organic compounds, with the exception of formic acid and formaldehyde, is worked. This procedure is characterized in that oxidation of the alcoholic - CH (OH) group occurs.
Es wurde nun gefunden, daß man sekundäre aliphatische bzw. heterocyklische Aminoalkohole dadurch in glatter Weise in am Stickstoff methylierte Derivate überführen kann, wobei eine solche Oxydation nicht stattfindet, daß man diese Basen mit Formaldehyd und Ameisensäure unter Druck in der Wärme behandelt. Es ist so z. B. möglich, in glatter Umsetzung aus i-(a'Pyrrolidyl)-Propan-i-ol die methylierte Hydraminbase zu erhalten. Die Reaktion erfolgt im Sinne der nachstehenden Gleichungen:It has now been found that secondary aliphatic or heterocyclic amino alcohols can be used can thus be converted smoothly into derivatives methylated on the nitrogen, where such an oxidation does not take place that these bases with formaldehyde and Heat treated formic acid under pressure. It is so z. B. possible in smoother Implementation from i- (a'Pyrrolidyl) -propan-i-ol to obtain the methylated hydramine base. The reaction is as follows Equations:
NHNH
-CH(OH). C2H5+ CH2O +H-COOH-CH (OH). C 2 H 5 + CH 2 O + H-COOH
-CH(O H)-C2H5+ H-COOH N-CH2OH-CH (OH) -C 2 H 5 + H-COOH N-CH 2 OH
= x /-CH(O H)- C2H5 + CO2 + H2O.= x / -CH (OH) -C 2 H 5 + CO 2 + H 2 O.
I N-CH.I N-CH.
Das neue Verfahren bildet einen einfachen Weg, um die bis jetzt nur mühsam zu erreichende Methylierung der sekundären Aminoalkohole (Hydraminbasen) glatt durchzuführen.·The new method is a simple way of eliminating what has been difficult to achieve up to now Methylation of the secondary amino alcohols (hydramine bases) can be carried out smoothly.
Beispiel ι.Example ι.
Einwirkung von Formaldehyd auf
i-(a-Pyrrolidyl)-Propan-i-ol bei
Gegenwart von Ameisensäure.Exposure to formaldehyde
i- (a-Pyrrolidyl) -propan-i-ol at
Presence of formic acid.
Die Auflösung von 2,6 Teilen des Aminoalkohols in 6 Teilen Wasser wird mit einem Teil Ameisensäure und 1,8 Teilen 4oprozentiger Formaldehydlösung unter Druck 4 bis 5 Stunden auf 110 bis 125° erhitzt. Nach der Reaktion ist der Kesselinhalt dunkel gefärbt. The dissolution of 2.6 parts of the amino alcohol in 6 parts of water is carried out with a Part formic acid and 1.8 parts 4% strength Formaldehyde solution heated to 110 to 125 ° under pressure for 4 to 5 hours. To After the reaction, the contents of the kettle are darkly colored.
Es wird von etwas ausgeschiedenem Harz abfiltriert und, nach dem Alkalischmachen mit reichlich konzentrierter Natronlauge, die sich dabei abscheidende Base in Äther aufgenommen. Nach dem Trocknen über Kaliumcarbonat und' Abdunsten des Äthers, wobei der Äther Anteile der flüchtigen Base mitnahm, siedet diese konstant bei 83° (ölbad 113 bis 116°) unter 14 bis 15 mm Druck. Die Base ist in der Wärme in Wasser schwerer löslich als in der Kälte.It is filtered off from some precipitated resin and, after making it alkaline with plenty of concentrated sodium hydroxide solution, the base which is deposited is taken up in ether. After drying over potassium carbonate and 'evaporation of the ether, whereby If the ether took parts of the volatile base with it, it boils constantly at 83 ° (oil bath 113 to 116 °) under 14 to 15 mm pressure. The base is less soluble in water when it is hot than when it is cold.
Einwirkung von Formaldehyd auf Methyldiacetonalkamin bei Gegenwart von Ameisensäure. Die Auflösung von 3 Teilen Methyldiacetonalkamin Effect of formaldehyde on methyldiacetone alkamine in the presence of formic acid. The dissolution of 3 parts of methyldiacetone alkamine
CH, NH-CH,CH, NH-CH,
CH, CH2-CH(OH)
I
CH,CH, CH 2 -CH (OH)
I.
CH,
und 6 Teilen Wasser wird mit 2 Teilen Ameisensäure und 2 Teilen 40 prozentiger Formaldehydlösung unter Druck 4 bis 5 Stunden auf 120 bis 130 ° erhitzt. Nach Beendigung der Reaktion ist der Kesselinhalt etwas dunkel gefärbt. Nach dem Versetzen mit konzentrierter Natronlauge wird die sich dabei abscheidende Base mit Äther gesammelt und die ätherische Lösung über Kaliumcarbonat getrocknet. Nach Abdunsten des Äthers siedet das hinter bleibende öl konstant bei 90 ° unter 24 mm Druck. Die Baseand 6 parts of water is mixed with 2 parts of formic acid and 2 parts of 40 percent formaldehyde solution heated under pressure to 120 to 130 ° for 4 to 5 hours. After completion the reaction, the contents of the kettle are somewhat dark in color. After adding concentrated Caustic soda, the base which is deposited is collected with ether and the ethereal solution over potassium carbonate dried. After the ether has evaporated, the oil that remains behind boils constantly at 90 ° 24 mm print. The base
CH,CH,
N(CH3),N (CH 3 ),
CH, CH2-CH(OH)-CH3 CH, CH 2 -CH (OH) -CH 3
ist in der Wärme in Wasser schwerer löslich als in der Kälte und zeigt die charakteristischen Eigenschaften der Hydramine. 'is more difficult to dissolve in water than in the cold and shows the characteristic Properties of hydramines. '
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE297847C true DE297847C (en) |
Family
ID=552114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT297847D Active DE297847C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE297847C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE738817C (en) * | 1939-01-17 | 1943-09-02 | Ig Farbenindustrie Ag | Process for the preparation of condensation products of the pyrrolidine series |
| US2578787A (en) * | 1949-04-09 | 1951-12-18 | Rohm & Haas | Reduction of enamines |
| US2924606A (en) * | 1960-02-09 | Alpha - hydroxy - beta - trihalogen- |
-
0
- DE DENDAT297847D patent/DE297847C/de active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2924606A (en) * | 1960-02-09 | Alpha - hydroxy - beta - trihalogen- | ||
| DE738817C (en) * | 1939-01-17 | 1943-09-02 | Ig Farbenindustrie Ag | Process for the preparation of condensation products of the pyrrolidine series |
| US2578787A (en) * | 1949-04-09 | 1951-12-18 | Rohm & Haas | Reduction of enamines |
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