CH301700A - Process for the preparation of a new aromatic thioether. - Google Patents
Process for the preparation of a new aromatic thioether.Info
- Publication number
- CH301700A CH301700A CH301700DA CH301700A CH 301700 A CH301700 A CH 301700A CH 301700D A CH301700D A CH 301700DA CH 301700 A CH301700 A CH 301700A
- Authority
- CH
- Switzerland
- Prior art keywords
- thioether
- compound
- formula
- converted
- carboxyl group
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 6
- -1 aromatic thioether Chemical class 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims description 8
- 150000003568 thioethers Chemical class 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims 1
- 239000002246 antineoplastic agent Substances 0.000 claims 1
- 229940127089 cytotoxic agent Drugs 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Substances SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/22—O-Aryl or S-Aryl esters thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/08—Amines; Quaternary ammonium compounds containing oxygen or sulfur
- A01N33/10—Amines; Quaternary ammonium compounds containing oxygen or sulfur having at least one oxygen or sulfur atom directly attached to an aromatic ring system
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/02—Monothiocarbamic acids; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung eines neuen aromatischen Thioäthers. Das vorliegende Patent bezieht sich auf ein Verfahren zur Herstellung eines neuen aro matischen Thioäthers, nämlich des 2,4-Dioxy- phenyl- [ss- (2'-carboxy-phenoxyäthoxy) -äthyl] - thioäthers.
Dieser Thioä.ther hat eine starke Hemm wirkung auf das Bakterienwachstum sowie eine gewisse vermicide Wirkung und soll als Chemo- thera.peuticum Verwendung finden.
Das erfindungsgemässe Verfahren zur Her stellung des neuen ,aromatischen Thioäthers ist. dadurch gekennzeichnet, dass man auf eine Verbindung der Formel
EMI0001.0017
eine Verbindung der Formel
EMI0001.0018
wobei X und Y sich bei der Reaktion abspal tende Reste und R ein durch Hydrolyse in die Carboxylgruppe überführbares Radikal bedeu ten, einwirken lässt und dass man anschliessend im erhaltenen Thioäther R durch Hydrolyse in die Carboxylgruppe überführt.
Man kann beispielsweise auf einMetallsalz des 2,4-Dioxy-thiophenols (X = Me, z. B. Natrium, Kalium usw.) eine Verbindung der Formel II einwirken lassen, in welcher Y ein Halogen atom oder einen andern sich leicht abspalten- den Rest, wie z. B. einen Alkyl- oder Aryl- sulfonyloxyrest, bedeutet und R vorzugsweise eine Carbalkoxygruppe ist.
Es ist weiter auch möglich, das 2,4-Dioxy- thiophenol in Gegenwart eines basischen Kon densationsmittels mit einer Verbindung der Formel II umzusetzen.
Der auf diese Weise erhaltene 2,4-Dioxy- phenyl- [ss- (2'-carboxy-phenoxyäthoxy) -äthyl ] - thioäther bildet ein weisses Natriumsalz, wel ches bei 173 klar schmilzt.
<I>Beispiel:</I> 1,6 g Natrium werden in 100 cm3 abs. Äthanol gelöst. Die Lösung wird mit<B>10,O g</B> 2,4-Dioxy-thiophenol versetzt und unter Rüh ren 18,2 g ss- (o-Carbomethoxy-phenoxyäthoxy) - äthylchlorid zugefügt. Man lässt 15 Stunden bei Zimmertemperatur stehen, kocht dann noch 2 Stunden auf dem Dampfbad und ver dampft zur Trockne. Der Rückstand wird in Chloroform aufgenommen und die Chloro- formlösung mit Wasser gewaschen.
Nach dem Trocknen über Natriumsulfat wird das Lö sungsmittel abdestilliert und der Rückstand (26 g) in Äthanol gelöst und mit 13,5g Ka- liumhydroxyd in 15 cm3 Wasser versetzt. Das Ganze wird eine Stunde am Rückfluss gekocht, der Alkohol abdestilliert, der Rückstand in 250 cm3 Nasser gelöst und mit 2n-Salzsäure angesäuert. Die ausgefallene Säure wird in Äther aufgenommen und mit einer Natrium- alkoholatlösung versetzt.
Das so in. guter Ausbeute gewonnene Natriiunsalz des 2,4- Dioxy-pheny l- [ ss- (2'-carboxy-phenoxy-äthoxy)- äthyl]-thioäthers schmilzt aus Dioxan um kristallisiert bei 173 klar. Es ist gut löslich in Wasser, schlecht in Methanol und Äthanol und unlöslich in Aceton, Benzol und Petrol- äther.
Das Bleisalz der Säure schmilzt bei 143 bis 146 .
Process for the preparation of a new aromatic thioether. The present patent relates to a process for the preparation of a new aromatic thioether, namely 2,4-dioxyphenyl [ss- (2'-carboxy-phenoxyethoxy) ethyl] - thioether.
This thioether has a strong inhibitory effect on bacterial growth as well as a certain vermicidal effect and is said to be used as a chemothera.peuticum.
The inventive method for the manufacture of the new, aromatic thioether position is. characterized in that a compound of the formula
EMI0001.0017
a compound of the formula
EMI0001.0018
where X and Y are radicals which split off during the reaction and R is a radical which can be converted into the carboxyl group by hydrolysis, and that is then allowed to act in the thioether R obtained by hydrolysis into the carboxyl group.
For example, a metal salt of 2,4-dioxy-thiophenol (X = Me, e.g. sodium, potassium, etc.) can be acted on by a compound of the formula II in which Y a halogen atom or another can easily be split off Rest, such as B. an alkyl or aryl sulfonyloxy radical, and R is preferably a carbalkoxy group.
It is also possible to react the 2,4-dioxythiophenol in the presence of a basic condensation agent with a compound of the formula II.
The 2,4-dioxyphenyl- [ss- (2'-carboxy-phenoxyethoxy) -ethyl] thioether obtained in this way forms a white sodium salt, which melts at 173 clearly.
<I> Example: </I> 1.6 g sodium are in 100 cm3 abs. Dissolved ethanol. 10.0 g of 2,4-dioxy-thiophenol are added to the solution, and 18.2 g of ss- (o-carbomethoxyphenoxyethoxy) ethyl chloride are added with stirring. It is left to stand for 15 hours at room temperature, then boiled for another 2 hours on the steam bath and evaporated to dryness. The residue is taken up in chloroform and the chloroform solution is washed with water.
After drying over sodium sulfate, the solvent is distilled off and the residue (26 g) is dissolved in ethanol, and 13.5 g of potassium hydroxide in 15 cm3 of water are added. The whole thing is refluxed for one hour, the alcohol is distilled off, the residue is dissolved in 250 cm3 of water and acidified with 2N hydrochloric acid. The precipitated acid is taken up in ether and mixed with a sodium alcoholate solution.
The sodium salt of 2,4-dioxy-phenyl- [ss- (2'-carboxy-phenoxy-ethoxy) -ethyl] -thioether obtained in this way in good yield melts from dioxane to crystallize at 173 °. It is readily soluble in water, poorly in methanol and ethanol, and insoluble in acetone, benzene and petroleum ether.
The lead salt of the acid melts at 143 to 146.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH297993T | 1951-11-16 | ||
| CH301700T | 1951-11-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH301700A true CH301700A (en) | 1954-09-15 |
Family
ID=25733935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH301700D CH301700A (en) | 1951-11-16 | 1951-11-16 | Process for the preparation of a new aromatic thioether. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH301700A (en) |
-
1951
- 1951-11-16 CH CH301700D patent/CH301700A/en unknown
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