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DE120047C - - Google Patents

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Publication number
DE120047C
DE120047C DENDAT120047D DE120047DA DE120047C DE 120047 C DE120047 C DE 120047C DE NDAT120047 D DENDAT120047 D DE NDAT120047D DE 120047D A DE120047D A DE 120047DA DE 120047 C DE120047 C DE 120047C
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DE
Germany
Prior art keywords
ether
hydrochloric acid
morpholine
solution
heated
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DENDAT120047D
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German (de)
Publication of DE120047C publication Critical patent/DE120047C/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/023—Preparation; Separation; Stabilisation; Use of additives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

KAISERLICHESIMPERIAL

PATENTAMT,PATENT OFFICE,

M 120047 KLASSE \2p. M 120047 CLASS \ 2p.

Durch die Einwirkung von Aethylenbromid auf die Natriumsalze der Phenole erhält man Bromäthylalphyläther. Aus diesen lassen sich durch Einwirkung von Ammoniak oder primären Aminen Basen von der allgemeinen FormThe action of ethylene bromide on the sodium salts of the phenols is obtained Bromoethylalphylether. From these can be made by the action of ammonia or primary Amines bases of the general form

/CH2-C H2-O-Alphyl CH2-CH2-O. Alphyl / CH 2 -CH 2 -O-alphyl CH 2 -CH 2 -O. Alphyl

gewinnen. Aehnlich constituirte Verbindungen erhält man, wenn man auf Sulfamide bei Gegenwart von Alkali die Bromäthylalphyläther reagiren läfst. Es entstehen dann substituirte Sulfamide der Form.to win. Compounds with a similar structure are obtained by referring to sulfamides The presence of alkali causes the bromoethylalphyl ether to react. Substituted ones then arise Sulfamides of the form.

R-SO .N/R-SO. N /

CH2. O. Alphyl
C0. Alphyl CH 2 . O. Alphyl
C0 . Alphyl

Endlich lassen sich Monoalphyläther des Diäthanolamins und seiner Derivate von der FormFinally, monoalphyl ethers of diethanolamine and its derivatives can be obtained from the shape

R.N/CH2. CH2.0. Alphyl R. N / CH 2 . CH 2 .0. Alphyl

* iy\CH2- CH2OH* iy \ CH 2 - CH 2 OH

durch Einwirkung von Aethylenchlorhydrin auf die entsprechenden Derivate der Aminoäthylalphyläther erhalten.by the action of ethylene chlorohydrin on the corresponding derivatives of the aminoethylalphyl ether obtain.

Alle diese Verbindungen liefern beim Erhitzen mit Mineralsäuren, besonders Salzsäure und verdünnter Schwefelsäure, unter Abspaltung der Phenole Derivate des Morpholins oder dieses selbst.All of these compounds give when heated with mineral acids, especially hydrochloric and dilute acids Sulfuric acid, with elimination of the phenols, derivatives of morpholine or this itself.

Um das bisher nur aus dem schwer zugänglichen Diäthanolamin erhältliche Morpholin (vergl. die Patentschriften 95854 und 97102) zu gewinnen, kann man z. B. so verfahren, dafs man den Iminoäthylphenyläther (Weddige, Journ. f. pract. Chemie [2] 24, 242)About morpholine, which was previously only available from diethanolamine, which was difficult to access (See. The patents 95854 and 97102) to win, you can z. B. proceed so that one the iminoethylphenyl ether (Weddige, Journ. f. pract. Chemie [2] 24, 242)

NH. (CH2 · CH2 · O - C6HJ2 NH. (CH 2 • CH 2 • O - C 6 HJ 2

mit Salzsäure 6 Stunden auf i6o° erhitzt. Die salzsaure Lösung giebt beim Abdampfen direct fast reines Morpholinchlorhydrat.heated to 160 ° with hydrochloric acid for 6 hours. the Hydrochloric acid solution gives almost pure morpholine chlorohydrate directly on evaporation.

Vortheilhafter ist es, von einem Sulfamid, z. B. p-Toluolsulfamid, auszugehen. Dieses bringt man mit'Bromäthyl - β - naphtyläther bei Gegenwart von Alkali nach der Gleichung:It is more advantageous to use a sulfamide, e.g. B. p-toluenesulfamide, go out. This one brings with bromoethyl - β - naphthyl ether in the presence of alkali according to the equation:

C7 H7 -SO2. NH2 -f 2 CH2Br ■ CH2 · O · C10H7 + 2,Na OH =C 7 H 7 -SO 2 . NH 2 -f 2 CH 2 Br · CH 2 • O • C 10 H 7 + 2, Na OH =

10J 10 y

CH2 · C H2 -O- C10 H7 CH2CH2OC10H7 CH 2 • CH 2 -O- C 10 H 7 CH 2 CH 2 OC 10 H 7

zur Reaction (vergl. Patentschrift 105870). Man erhält dann glatt den Dinaphtyläther des p-Toluolsulfodiäthanolamids (Schmelzipunkt 1300). Diese Verbindung wird mit SaIzsäure von 25 pCt. im Autoklaven auf ca. 1700 etwa 8 Stunden erhitzt. Dabei vollzieht sich folgende Spaltung:for reaction (see patent specification 105870). One then obtains the smooth Dinaphtyläther of p-Toluolsulfodiäthanolamids (Schmelzipunkt 130: 0). This compound is with hydrochloric acid of 25 pCt. heated in the autoclave to about 170 0 for about 8 hours. The following split takes place:

C7H7. SO2 N: (CH2 · CH2 · O ■ C10H7J2 + -X1H2O = H2SO, + 2C10HO+ HN( C 7 H 7 . SO 2 N: (CH 2 CH 2 O ■ C 10 H 7 J 2 + -X 1 H 2 O = H 2 SO, + 2C 10 HO + HN (

C7H8 C 7 H 8

Claims (1)

so dafs Toluol, Schwefelsäure, Naphtol und Morpholin gebildet wird.so that toluene, sulfuric acid, naphthol, and morpholine are formed. Aus dem Reactionsproduct läfst sich das Morpholin in Form des Chlorhydrats so isoliren, dafs man nach Abfiltriren des in Wasser unlöslichen Antheiles und Entfernen der Schwefelsäure durch die äquivalente Menge Baryumcarbonat eindampft, wobei salzsaures Morpholin in Krystallen hinterbleibt. Aus dem Salze läfst sich die Base in der üblichen Weise isoliren. -The morpholine can thus be derived from the reaction product in the form of the chlorohydrate isolate that after filtering off the water-insoluble portion and removing it the sulfuric acid evaporated by the equivalent amount of barium carbonate, with hydrochloric acid Morpholine remains in crystals. The base can be removed from the salt in the usual way isolate. - Will man endlich zur Darstellung des Morpholins von Aminoäthylphenyläther (Schmidt, Ber. d. D. ehem. Ges. 22, 3256) ausgehen, so ■läfst man auf diese Verbindung ρ - Toluolsulfochlorid bei Gegenwart von Alkali einwirken und erhält so in üblicher Weise den p-Toluols ulfoaminoä thy lpheny lätherIf one finally wants to represent the morpholine of aminoethylphenyl ether (Schmidt, Ber. d. D. former Ges. 22, 3256), one leads to this compound ρ - toluenesulfochloride act in the presence of alkali and thus obtain the p-toluene in the usual way ulfoaminoä thy lpheny ether C7H7-SO2-NH-CH2.C 7 H 7 -SO 2 -NH-CH 2 . CH2-O- C6H5 CH 2 -O- C 6 H 5 (Schmelzpunkt 104). Diese Verbindung liefert beim Kochen mit der äquivalenten Menge Kalihydrat und Aethylenchlorhydrin in alkoholischer Lösung den M onophenyläther des p-Toluolsulfodiäthanoiamids(Melting point 104). This compound delivers when cooked with the equivalent amount Potassium hydrate and ethylene chlorohydrin in alcoholic solution the monophenyl ether of p-toluene sulfodiethanoiamide Γ H SO NyCHi'CHi'0H
o7J«7ou2iv χ ^ CH2-CH2-O-C6H5 Γ H SO N yCH i ' CH i' 0H
o 7J « 7 ou 2 iv χ ^ CH 2 -CH 2 -OC 6 H 5 (Schmelzpunkt 73), welch letzteres beim Erhitzen mit Salzsäure ganz analog dem oben beschriebenen Dinaphtyläther reagirt. Zur Darstellung von Methylmorpholin kann man z. B. vom Methyliminoäthylphenylä'ther ■■■.. CH3N(CH2 - CH- O - C6HJ2 (Melting point 73), which, when heated with hydrochloric acid, reacts analogously to the dinaphthyl ether described above. For the representation of methylmorpholine you can, for. B. from methyliminoethylphenyl ether ■■■ .. CH 3 N (CH 2 - CH - O - C 6 HJ 2 ausgehen, welcher man durch Einwirkung von Bromäthylphenyläther auf eine wässerig-alkoholische Methylarninlösung bei ioo° erhält. Das Reactionsproduct wird nach dem Abdestilliren des Alkohols und Methylamins mit starkem, wässerigem Alkali versetzt, worauf, sich ein Gemenge von Methylaminoäthylphenylä'ther CH5NHCH2 - CH2 - O - C6H5 und Methyliminoäthylphenyläther CHz(NCH2-CH2-O-C6HJ2 go out, which is obtained by the action of bromoethylphenyl ether on an aqueous-alcoholic methylamine solution at 100 °. After the alcohol and methylamine have been distilled off, the reaction product is treated with strong, aqueous alkali, whereupon a mixture of methylaminoethylphenyl ether CH 5 NHCH 2 - CH 2 - O - C 6 H 5 and methyliminoethylphenyl ether CH2 (NCH 2 -CH 2 - OC 6 HJ 2 abscheidet. Zur Trennung dieser Basen versetzt man ihre salzsaure Lösung mit Natriumnitrit, bis dieselbe nach einigem Stehen Jodstärkepapier bläut. Dabei scheidet sich die Nitrosoverbindung der seeundären Base ab. Aus der salzsauren Lösung wird sodann durch starke Alkalilauge die tertiäre Base abgeschieden.separates. To separate these bases, their hydrochloric acid solution is mixed with sodium nitrite, until after standing for a while it turns blue on iodine starch paper. This divides the Nitroso compound from the secondary base. The hydrochloric acid solution then becomes through strong Alkali solution deposited the tertiary base. Diese wird ohne weitere Reinigung mit Salzsäure 6 Stunden auf ca. i6o° erhitzt, wobei sie in Phenol und Methylmorpholin zerfällt. Beim Abdampfen der salzsauren Lösung bleibt fast reines Methylmorpholinchlorhydrat zurück.This is heated to about 160 ° for 6 hours without further purification with hydrochloric acid, with it breaks down into phenol and methylmorpholine. When the hydrochloric acid solution evaporates, it remains almost pure methylmorpholine chlorohydrate. Patenτ-Ansprdch:Patent claim: Die Darstellung des Morpholins und seiner Derivate dadurch, dafs man Mono- oder Dialphyläther des Diäthanolamins oder deren Derivate mit Mineralsäuren erhitzt.The preparation of morpholine and its derivatives by using mono- or dialphyl ethers of diethanolamine or its derivatives heated with mineral acids.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001068592A1 (en) * 2000-03-13 2001-09-20 Eli Lilly And Company Sulfonamide derivatives
EP1389183B1 (en) * 2001-05-14 2010-03-03 Novartis AG Sulfonamide derivatives

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001068592A1 (en) * 2000-03-13 2001-09-20 Eli Lilly And Company Sulfonamide derivatives
US6911476B2 (en) 2000-03-13 2005-06-28 Eli Lilly And Company Sulfonamide derivatives
EP1389183B1 (en) * 2001-05-14 2010-03-03 Novartis AG Sulfonamide derivatives

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