DE1007322B - Process for the production of sulfur-containing basic esters - Google Patents
Process for the production of sulfur-containing basic estersInfo
- Publication number
- DE1007322B DE1007322B DEM29770A DEM0029770A DE1007322B DE 1007322 B DE1007322 B DE 1007322B DE M29770 A DEM29770 A DE M29770A DE M0029770 A DEM0029770 A DE M0029770A DE 1007322 B DE1007322 B DE 1007322B
- Authority
- DE
- Germany
- Prior art keywords
- ethanol
- sulfur
- diethylaminoethylthio
- carboxylic acid
- containing basic
- 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.)
- Granted
Links
Classifications
-
- 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
- C07D295/16—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 acylated on ring nitrogen atoms
- C07D295/20—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 acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
- C07D295/205—Radicals derived from carbonic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/25—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
DEUTSCHESGERMAN
Die Erfindung bezieht sich auf die Herstellung organischer Ester der allgemeinen FormelThe invention relates to the preparation of organic esters of the general formula
^—C — COOCH2CH2- S — CH2CH2N (C2H5)2 ^ - C - COOCH 2 CH 2 - S - CH 2 CH 2 N (C 2 H 5 ) 2
IiIi
worin R die Reste — (CH9Jn — oder — (CH2)2 — O —-(CH2)2 — und η = 2 bis 5 bedeuten, und deren Salze mit einer organischen oder Mineralsäure.where R is the radicals - (CH 9 J n - or - (CH 2 ) 2 - O - (CH 2 ) 2 - and η = 2 to 5, and their salts with an organic or mineral acid.
Diese Ester besitzen eine beträchtliche Antihustenwirkung, welche derjenigen des Codeins um das I1Z2fache überlegen ist. Gegenüber dem Codein und seinen Derivaten besitzen die Produkte der Erfindung außerdem die wesentlichen Vorteile, daß sie nicht betäubend wirken, keine Verstopfung hervorrufen und nicht süchtig machen.These esters have a considerable anti-cough effect, which is I 1 Z 2 times superior to that of codeine. Compared to codeine and its derivatives, the products of the invention also have the essential advantages that they do not have an anesthetic effect, do not cause constipation and are not addictive.
Gemäß der vorliegenden Erfindung stellt man diese Ester her, indem man das 2-(2'-Diäthylaminoäthylthio)-äthanol mit einer Verbindung der allgemeinen FormelAccording to the present invention, these esters are prepared by adding 2- (2'-diethylaminoethylthio) ethanol with a compound of the general formula
Verfahren zur Herstellung
schwefelhaltiger basischer EsterMethod of manufacture
sulfur-containing basic ester
Anmelder:Applicant:
Dr. Henri Morren,Dr. Henri Morren,
Forest, Brüssel (Belgien)Forest, Brussels (Belgium)
Vertreter: Dr.-Ing. A. van der Werth, Patentanwalt,
Hamburg-Harburg 1, Wilstorfer Str. 32Representative: Dr.-Ing. A. van der Werth, patent attorney,
Hamburg-Harburg 1, Wilstorfer Str. 32
Beanspruchte Priorität:
Belgien vom 26, Februar 1955Claimed priority:
Belgium from February 26, 1955
Dr. Henri Morren, Forest, Brüssel (Belgien),
ist als Erfinder genannt wordenDr. Henri Morren, Forest, Brussels (Belgium),
has been named as the inventor
-C —COR'-C —COR '
reagieren läßt, in welcher R die gleiche Bedeutung wie oben hat und R' ein Chloratom, eine Hydroxylgruppe oder eine Gruppe —OR" darstellt, in der R" einen Alkylrest mit 1 bis 3 Kohlenstoffatomen bedeutet.lets react, in which R has the same meaning as above and R 'is a chlorine atom, a hydroxyl group or a group —OR "in which R" denotes an alkyl radical having 1 to 3 carbon atoms.
Wenn man als Ausgangsprodukt ein Säurechlorid verwendet, kann die Reaktion in Gegenwart eines Chlorwasserstoff bindenden Mittels durchgeführt werden. Bei einem Ester findet Bildung von Methanol, Äthanol oder Propanol statt, welches bei der Reaktionstemperatur abdestilliert.If an acid chloride is used as the starting material, the reaction in the presence of a can Hydrogen chloride binding agent can be carried out. In the case of an ester, there is formation of methanol, ethanol or propanol instead, which distills off at the reaction temperature.
Die folgenden Beispiele erläutern die Erfindung.The following examples illustrate the invention.
1 -Phenylcyclopentan-1 -carbonsäureester
des 2-(2'-Diäthylaminoäthylthio)-äthanols1-phenylcyclopentane-1-carboxylic acid ester
of 2- (2'-diethylaminoethylthio) ethanol
/ V-C-COOCH2CH2-S- CH2-CH2N(C2Hg)2 / VC-COOCH 2 CH 2 -S- CH 2 -CH 2 N (C 2 Hg) 2
H9CH 9 C
CH,CH,
sie mit Kaliumcarbonat und engt sie im Vakuum ein. Der Rückstand wird im Vakuum fraktioniert destilliert. Man erhält den 1-Phenylcyclopentan-1-carbonsäureester des 2-(2'-Diäthylaminoäthylthio)-äthanols. Kp. 0,05= 190 bis 193°; Ausbeute 50%.them with potassium carbonate and concentrate them in a vacuum. The residue is fractionally distilled in vacuo. The 1-phenylcyclopentane-1-carboxylic acid ester is obtained of 2- (2'-diethylaminoethylthio) ethanol. B.p. 0.05 = 190 to 193 °; Yield 50%.
Man stellt das saure Citrat des Esters durch Zusatz einer konzentrierten alkoholischen Citronensäurelösung zu einer Ätherlösung des Esters her. Schmelzpunkt des Citrats: 98°.The acidic citrate of the ester is prepared by adding a concentrated alcoholic citric acid solution to an ethereal solution of the ester. Melting point of the citrate: 98 °.
1 -Phenylcyclopropan-l -carbonsäureester
des 2-(2'-Diäthylaminoäthylthio)-äthanols1-phenylcyclopropane-l -carboxylic acid ester
of 2- (2'-diethylaminoethylthio) ethanol
3535
H2 C CH2 H 2 C CH 2
Eine Mischung von 0,5 Mol 1-Phenylcyclopentan-1-carbonsäurechlorid und 0,5 Mol von 2-(2'-Diäthylaminoäthylthio)-äthanol in 300 ecm Toluol wird am Rückflußkühler 20 Stunden erhitzt.A mixture of 0.5 moles of 1-phenylcyclopentane-1-carboxylic acid chloride and 0.5 mol of 2- (2'-diethylaminoäthylthio) ethanol in 300 ecm of toluene is on Heated reflux condenser for 20 hours.
Man macht dann das Gemisch mit einer wäßrigen 5%igen Natriumhydroxydlösung alkalisch. Man trennt die Toluollösung ab, wäscht sie mit Wasser, trocknet ^-C — COOCH2CH2 -S-- CH2CH2N(C2H6 The mixture is then made alkaline with an aqueous 5% sodium hydroxide solution. The toluene solution is separated off, washed with water, dried ^ -C - COOCH 2 CH 2 -S-- CH 2 CH 2 N (C 2 H 6
H2CH 2 C
-CH9 -CH 9
Er wird nach Beispiel 1 durch Reaktion von 1-Phenylcyclopropan-l-carbonsäurechlorid und 2-(2'-Diäthylaminoäthylthio)-äthanol hergestellt. Kp. Oox = 150 bis 155°.It is prepared according to Example 1 by reacting 1-phenylcyclopropane-1-carboxylic acid chloride and 2- (2'-diethylaminoethylthio) ethanol. Bp. O ox = 150 to 155 °.
1 -Phenylcyclobutan-1 -carbonsäureester1-phenylcyclobutane-1-carboxylic acid ester
des 2-(2'-Diäthylaminoäthylthio)-äthanolsof 2- (2'-diethylaminoethylthio) ethanol
i \-C — COOCH2CH2- S — CH2CH2N(C2H6)2 i \ -C - COOCH 2 CH 2 - S - CH 2 CH 2 N (C 2 H 6 ) 2
C
H2 C.
H 2
709 »7/432709 »7/432
Es wird nach Beispiel 1 durch Reaktion von 1-Phenylcyclobutan-1-carbonsäurechlorid und 2-(2'-Diäthylarninoäthylthio)-äthanol hergestellt. Kp. 0,oo5 = 150 bis 155°.It is prepared according to Example 1 by reacting 1-phenylcyclobutane-1-carboxylic acid chloride and 2- (2'-diethylarninoethylthio) ethanol. Kp. 0 , oo5 = 150 to 155 °.
4-Phenyltetrahydropyran-4-carbonsäureester des 2-(2'-Diäthylaminoäthylthio)-äthanols4-phenyltetrahydropyran-4-carboxylic acid ester of 2- (2'-diethylaminoethylthio) ethanol
—C — COOCH2CH2-S- CH2CH2N(C2Hg)2 - C - COOCH 2 CH 2 -S- CH 2 CH 2 N (C 2 Hg) 2
0,2 g Natrium zu, führt dann 20,1 g des Äthylesters der0.2 g of sodium then leads to 20.1 g of the ethyl ester
• l-Phenylcyclohexan-l-carbonsäure ein und erwärmt das Gemisch allmählich 2 bis 3 Stunden unter langsamem• l-phenylcyclohexane-l-carboxylic acid and heats the Mix gradually for 2 to 3 hours under slow
Abdestillieren des sich bildenden Äthanols und des Xylols, bis eine Temperatur von 140° erreicht ist.Distilling off the ethanol that forms and the xylene until a temperature of 140 ° is reached.
Man behandelt den Rückstand mit Benzol, wäscht ihn mit Wasser und dekantiert ihn dann. Man trocknet die Benzollösung, treibt das Lösungsmittel ab und destilliert dann. Man erhält 12,2 g des Esters, welcher bei Kp. 01 = 190 bis 195° destilliert.The residue is treated with benzene, washed with water and then decanted. The benzene solution is dried, the solvent is driven off and then distilled. This gives 12.2 g of the ester, which in Kp. Distilled 0 1 = 190 ° to 195 °.
CH,CH,
Es wird nach Beispiel 1 durch Reaktion von 4-Phenyltetrahydropyran-4-carbonsäurechlorid und 2-(2'-Diäthylaminoäthylthio)-äthanol hergestellt. Kp. 005= 185 bis 190°. aoIt is made according to Example 1 by reacting 4-phenyltetrahydropyran-4-carboxylic acid chloride and 2- (2'-diethylaminoethylthio) ethanol prepared. Kp. 005 = 185 to 190 °. ao
l-Phenylcyclohexan-l-carbonsäureester des 2-(2'-Diäthylaminoäthylthio)-äthanolsL-phenylcyclohexane-l-carboxylic acid ester of 2- (2'-diethylaminoethylthio) ethanol
"V-C-COOCh2CH2-S-CH2CH2N(C2Hb)2 *5 "CH9 "VC-COOCh 2 CH 2 -S-CH 2 CH 2 N (C 2 Hb) 2 * 5 " CH 9
H9CH 9 C
H2CH 2 C
CH9 CH 9
C
H2 C.
H 2
Man stellt den Äthylester der 1-Phenylcyclohexan-1-carbonsäure her, indem man Chlorwasserstoff in eine Äthanollösung der Säure einleitet. Man setzt Wasser zu, dekantiert den Ester, welcher sich abgetrennt hat, trocknet und destilliert ihn dann. Siedepunkt des Äthylesters Kp.0,i = 100 bis 105°.The ethyl ester of 1-phenylcyclohexane-1-carboxylic acid is prepared by introducing hydrogen chloride into an ethanol solution of the acid. Water is added, the ester which has separated off is decanted, dried and then distilled. Boiling point of the ethyl ester bp. 0 , i = 100 to 105 °.
Man stellt eine Lösung von 17,7 g des 2-(2'-Diäthyl- 4<> aminoäthylthio)-äthanols in 60 ecm Xylol her, setztA solution of 17.7 g of 2- (2'-diethyl- 4 <> aminoäthylthio) ethanol in 60 ecm xylene, sets
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE805704X | 1955-02-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE1007322C2 DE1007322C2 (en) | 1957-10-10 |
| DE1007322B true DE1007322B (en) | 1957-10-10 |
Family
ID=37387860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1956M0029770 Expired DE1007322C2 (en) | 1955-02-28 | 1956-02-24 | Process for the production of sulfur-containing basic esters |
Country Status (4)
| Country | Link |
|---|---|
| CH (1) | CH336378A (en) |
| DE (1) | DE1007322C2 (en) |
| GB (1) | GB805704A (en) |
| NL (1) | NL90725C (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB646204A (en) * | 1947-07-01 | 1950-11-15 | Geigy Ag J R | Manufacture of new basic esters of 1-aryl-cycloalkyl-1-monothio-carboxylic acids |
| CH274379A (en) * | 1947-05-23 | 1951-03-31 | Ag J R Geigy | Process for the preparation of a new basic ester of a 1-aryl-cyclopentane-1-monothio-carboxylic acid. |
| US2674615A (en) * | 1952-06-28 | 1954-04-06 | Abbott Lab | 1-arylcycloalkane 1-thiocar-boxylates |
-
1956
- 1956-01-21 NL NL203820A patent/NL90725C/xx active
- 1956-02-21 GB GB5382/56A patent/GB805704A/en not_active Expired
- 1956-02-22 CH CH336378D patent/CH336378A/en unknown
- 1956-02-24 DE DE1956M0029770 patent/DE1007322C2/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH274379A (en) * | 1947-05-23 | 1951-03-31 | Ag J R Geigy | Process for the preparation of a new basic ester of a 1-aryl-cyclopentane-1-monothio-carboxylic acid. |
| GB646204A (en) * | 1947-07-01 | 1950-11-15 | Geigy Ag J R | Manufacture of new basic esters of 1-aryl-cycloalkyl-1-monothio-carboxylic acids |
| US2674615A (en) * | 1952-06-28 | 1954-04-06 | Abbott Lab | 1-arylcycloalkane 1-thiocar-boxylates |
Also Published As
| Publication number | Publication date |
|---|---|
| GB805704A (en) | 1958-12-10 |
| DE1007322C2 (en) | 1957-10-10 |
| CH336378A (en) | 1959-02-28 |
| NL90725C (en) | 1958-11-15 |
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