DE1134070B - Process for the production of sulfonic acid derivatives - Google Patents
Process for the production of sulfonic acid derivativesInfo
- Publication number
- DE1134070B DE1134070B DEF32832A DEF0032832A DE1134070B DE 1134070 B DE1134070 B DE 1134070B DE F32832 A DEF32832 A DE F32832A DE F0032832 A DEF0032832 A DE F0032832A DE 1134070 B DE1134070 B DE 1134070B
- Authority
- DE
- Germany
- Prior art keywords
- sulfonic acid
- acid derivatives
- production
- derivatives
- ester
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 6
- 150000003458 sulfonic acid derivatives Chemical class 0.000 title claims description 3
- 239000002253 acid Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- 239000003701 inert diluent Substances 0.000 claims 1
- 239000012442 inert solvent Substances 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 3
- STZZWJCGRKXEFF-UHFFFAOYSA-N Dichloroacetonitrile Chemical compound ClC(Cl)C#N STZZWJCGRKXEFF-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- HKMLRUAPIDAGIE-UHFFFAOYSA-N methyl 2,2-dichloroacetate Chemical compound COC(=O)C(Cl)Cl HKMLRUAPIDAGIE-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- AQJYJFZSNMNVLN-UHFFFAOYSA-N n,n-diethylethenesulfonamide Chemical compound CCN(CC)S(=O)(=O)C=C AQJYJFZSNMNVLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- SIEILFNCEFEENQ-UHFFFAOYSA-N dibromoacetic acid Chemical compound OC(=O)C(Br)Br SIEILFNCEFEENQ-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- JOXWSDNHLSQKCC-UHFFFAOYSA-N ethenesulfonamide Chemical class NS(=O)(=O)C=C JOXWSDNHLSQKCC-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- FUOMAVUUVFKRCF-UHFFFAOYSA-N propyl ethenesulfonate Chemical compound CCCOS(=O)(=O)C=C FUOMAVUUVFKRCF-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 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
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B45/00—Formation or introduction of functional groups containing sulfur
- C07B45/02—Formation or introduction of functional groups containing sulfur of sulfo or sulfonyldioxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/70—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a carbon skeleton substituted by carboxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Sulfonsäurederivaten y-Sulfonsäurederivate der a, a-Dihalogenbuttersäure bzw. ihrer Ester sind in der Literatur nicht bekannt.Process for the preparation of sulfonic acid derivatives γ-sulfonic acid derivatives α, α-dihalobutyric acid or its esters are not known in the literature.
Es wurde gefunden, daß man diese Verbindungen dadurch herstellen kann, daß man funktionelle Derivate der Dihalogenessigsäuren, z. B. Amide, Ester oder Nitrile, an a,ß-ungesättigte Sulfonsäuren oder deren funktionelle Derivate in Gegenwart von alkalischen Mitteln anlagert. It has been found that these compounds can be made in this way can that one functional derivatives of dihaloacetic acids, z. B. amides, esters or nitriles, α, β-unsaturated sulfonic acids or their functional derivatives accumulates in the presence of alkaline agents.
So erhält man z. B. aus Vinylsulfonsäureester und Dichloressigester in Gegenwart von Alkalialkoholaten a,a-Dichlor-y-alkoxysulfonylbuttersäureester. An Stelle der Vinylsulfonsäureester kann man auch Vinylsulfonsäureamide und substituierte Vinylsulfonsäurederivate verwenden. Der Dichloressigester ist bei dieser Reaktion z. B. durch Dichloracetonitril, Dibromessigester ersetzbar. Als alkalische Kondensationsmittel eignen sich in erster Linie Alkalialkoholate, z. B. Natriummethylat. Es genügen dabei schon katalytische Mengen; man kann aber, besonders bei niedrigen Reaktionstemperaturen, auch größere Alkalialkoholatmengen verwenden, ohne daß Nebenreaktionen stattfinden. Die Anlagerungsreaktion verläuft exotherm. Sie kann in Anwesenheit oder Abwesenheit eines Lösungs-oder Verdünnungsmittels, wie Benzol oder Toluol, durchgeführt werden. So you get z. B. from vinyl sulfonic acid ester and dichloroacetic ester in the presence of alkali alcoholates a, a-dichloro-y-alkoxysulfonylbutyric acid ester. Instead of vinyl sulfonic acid esters, vinyl sulfonic acid amides and substituted ones can also be used Use vinyl sulfonic acid derivatives. The dichloroacetic ester is involved in this reaction z. B. can be replaced by dichloroacetonitrile, dibromoacetate. As an alkaline condensing agent are primarily alkali metal alcoholates, e.g. B. sodium methylate. It is enough at the same time catalytic amounts; but you can, especially at low reaction temperatures, also use larger amounts of alkali metal alcoholate without side reactions taking place. The addition reaction is exothermic. It can be present or absent a solvent or diluent, such as benzene or toluene, can be carried out.
Es war nicht zu erwarten, daß die erfindungsgemäße Reaktion im beschriebenen Sinne verlaufen würde. Vielmehr war zu erwarten, daß Esterkondensationen oder Austausch von Halogen gegen Alkoxygruppen stattfinden würden. It was not to be expected that the reaction according to the invention in the described Senses would run. Rather, it was to be expected that ester condensations or exchanges of halogen versus alkoxy groups would take place.
Die Erzeugnisse des erfindungsgemäßen Verfahrens sind beständige Verbindungen; soweit sie nicht fest sind, lassen sie sich unzersetzt destillieren. The products of the process according to the invention are stable Links; if they are not solid, they can be distilled without decomposition.
Sie können als Ausgangsmaterialien für zahlreiche Synthesen, z. B. von Arzneimitteln und Pflanzenschutzmitteln, dienen.They can be used as starting materials for numerous syntheses, e.g. B. of pharmaceuticals and pesticides.
Beispiel 1 150 g Vinylsulfonsäurepropylester (1 Mol) wurden zusammen mit 143 g Dichloressigsäuremethylester (1 Mol) in 500ccm Toluol gelöst; zu der Lösung wurden unter Rühren langsam 6g festes Natriummethylat gegeben. Die exotherme Reaktion wurde durch Kühlung so geleitet, daß die Temperatur 40° C nicht überschritt. Nach mehrstündigem Rühren bei Zimmertemperatur wurde mit Äther versetzt und mit verdünnter Essigsäure neutral gewaschen. Example 1 150 g of propyl vinyl sulfonate (1 mole) were added together with 143 g of methyl dichloroacetate (1 mol) dissolved in 500ccm of toluene; to the solution 6 g of solid sodium methylate were slowly added with stirring. The exothermic reaction was passed through cooling so that the temperature did not exceed 40.degree. To stirring for several hours at room temperature was mixed with ether and diluted with Acetic acid washed neutral.
Nach Trocknen der organischen Phase über Natriumsulfat wurde destilliert Kp.o,os mm = 128 bis 1300 C, Ausbeute 220 g, entsprechend 750/0 der Theorie an y-Propoxysulfonyl- a,a- dichlorbuttersäuremethylester der Formel Beispiel 2 Eine Lösung von 163 g Vinylsulfonsäurediäthylamid und 143 g Dichloressigsäuremethylester in 500 ccm Toluol wurde, wie im vorstehenden Beispiel beschrieben, mit 6 g Natriummethylat versetzt. Die Aufarbeitung erfolgte ebenfalls wie im vorstehenden Beispiel. 220 g r-Diäthylamidosulfonyl-a,a-dichlorbuttersäuremethylester, Kp.l = 154 bis 1550 C und F. = 37° C, der Formel wurden erhalten.After the organic phase had been dried over sodium sulfate, it was distilled, boiling point os mm = 128 to 1300 ° C., yield 220 g, corresponding to 750/0 of theory, of methyl y-propoxysulfonyl-a, a-dichlorobutyrate of the formula EXAMPLE 2 A solution of 163 g of vinylsulphonic acid diethylamide and 143 g of methyl dichloroacetate in 500 cc of toluene was admixed with 6 g of sodium methylate as described in the above example. Work-up was also carried out as in the previous example. 220 g of methyl r-diethylamidosulfonyl-a, a-dichlorobutyrate, boiling point = 154 to 1550 ° C. and melting point = 37 ° C., of the formula were received.
Analog erhält man den y-Morpholidosulfonyla,a-dichlorbuttersäuremethylester, F. = 910 C, in 71 Obiger Ausbeute. The y-morpholidosulfonyla, a-dichlorobutyric acid methyl ester, is obtained analogously, F. = 910 C, in 71 above yield.
Beispiel 3 Eine Lösung von 163 g Vinylsulfonsäurediäthylamid und 110 g Dichloracetonitril in 500 ccm Toluol wurde, wie oben beschrieben, mit 6 g Natriummethylat versetzt und aufgearbeitet. Man erhielt 190 g y-Diäthylamidosulfonyl-a, a-dichlor butyronitril, Kp.0,3 mm = 1280 C. Example 3 A solution of 163 g of vinylsulfonic acid diethylamide and 110 g of dichloroacetonitrile in 500 ccm of toluene was, as described above, with 6 g Sodium methylate is added and worked up. Man received 190 g of γ-diethylamidosulfonyl-a, a-dichlorobutyronitrile, bp 0.3 mm = 1280 C.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF32832A DE1134070B (en) | 1960-12-23 | 1960-12-23 | Process for the production of sulfonic acid derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF32832A DE1134070B (en) | 1960-12-23 | 1960-12-23 | Process for the production of sulfonic acid derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1134070B true DE1134070B (en) | 1962-08-02 |
Family
ID=7094811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF32832A Pending DE1134070B (en) | 1960-12-23 | 1960-12-23 | Process for the production of sulfonic acid derivatives |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1134070B (en) |
-
1960
- 1960-12-23 DE DEF32832A patent/DE1134070B/en active Pending
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