DE2257148B2 - Phenylamidosulfonyl-phenoxy-acetic acids and process for their preparation - Google Patents

Phenylamidosulfonyl-phenoxy-acetic acids and process for their preparation

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Publication number
DE2257148B2
DE2257148B2 DE19722257148 DE2257148A DE2257148B2 DE 2257148 B2 DE2257148 B2 DE 2257148B2 DE 19722257148 DE19722257148 DE 19722257148 DE 2257148 A DE2257148 A DE 2257148A DE 2257148 B2 DE2257148 B2 DE 2257148B2
Authority
DE
Germany
Prior art keywords
preparation
phenylamidosulfonyl
phenoxy
chlorophenoxyacetic acid
acid
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
Application number
DE19722257148
Other languages
German (de)
Other versions
DE2257148A1 (en
DE2257148C3 (en
Inventor
Gheorghe Botez
Cornelia Gorea
Ecaterina Merica
Corneliu Oniscu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FABRICA DE ANTIBIOTICE IASI IASI (RUMAENIEN)
Original Assignee
FABRICA DE ANTIBIOTICE IASI IASI (RUMAENIEN)
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by FABRICA DE ANTIBIOTICE IASI IASI (RUMAENIEN) filed Critical FABRICA DE ANTIBIOTICE IASI IASI (RUMAENIEN)
Priority to DE19722257148 priority Critical patent/DE2257148C3/en
Priority claimed from DE19722257148 external-priority patent/DE2257148C3/en
Publication of DE2257148A1 publication Critical patent/DE2257148A1/en
Publication of DE2257148B2 publication Critical patent/DE2257148B2/en
Application granted granted Critical
Publication of DE2257148C3 publication Critical patent/DE2257148C3/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/78—Halides of sulfonic acids
    • C07C309/86—Halides of sulfonic acids having halosulfonyl groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/87—Halides of sulfonic acids having halosulfonyl groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/22—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound oxygen atoms
    • C07C311/29—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound oxygen atoms having the sulfur atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring

Description

Es sind Sulfamide der Phenoxyessigsäure und Phenoxypropionsäuren sowie Sulfamide der Phenoxybuttersäuren und Kresoxybuttersäuren bekannt, welche durch Chlorsulfonierungmit Chlorsulfonsäureüberschuß, Amidierung und Hydrolyse erhalten werden.There are sulfamides of phenoxyacetic acid and phenoxypropionic acids and sulfamides of phenoxybutyric acids and cresoxybutyric acids known, which by chlorosulfonation with chlorosulfonic acid excess, Amidation and hydrolysis can be obtained.

Die erfindungsgemäßen Phenylamidosulfonyl-phenoxyessigsäuren, die wie im Anspruch erläutert, hergestellt werden, bereichern die Skala von Substanzen mit Anregungswirkungen bei Biosyntheseprozessen der Penicillinherstellung. Sie bewirken eine Erhöhung der Aktivität in der Kulturflüssigkeit mit 20 bis 30% im Vergleich zu den bekannten Anregern.The phenylamidosulfonyl-phenoxyacetic acids according to the invention, which are produced as explained in the claim enrich the range of substances with stimulating effects in biosynthetic processes of penicillin production. They cause an increase the activity in the culture liquid with 20 to 30% compared to the known stimulators.

Sie entsprechen der allgemeinen FormelThey correspond to the general formula

SO,NHSO, NH

HOOC-CH2-OHOOC-CH 2 -O

wobei R gemäß den Ansprüchen 1 bis 4 Chlor (2-, 3- oder 4-Stellung) oder Methyl (4-Stellung) ist. Sie sind weiße, beständige Stoffe, die nichttoxisch sind.where R according to claims 1 to 4 is chlorine (2-, 3- or 4-position) or methyl (4-position). They are white, permanent fabrics that are non-toxic.

Nr. Chemische BezeichnungNo. Chemical name

SchmelzpunktMelting point

1 2-(4-ChJoiphenylamidosulfonyl)- 209
4-chlor-phenoxyessigsäure1 2- (4-ChJoiphenylamidosulfonyl) - 209
4-chloro-phenoxyacetic acid

2 2-(3-Chlorphenylamidosulfonyl)- 183
4-chlor-phenoxyessigsäure2 2- (3-chlorophenylamidosulfonyl) - 183
4-chloro-phenoxyacetic acid

3 2-{2-Chlorphenylamidosulfonyl)- 162
4-chlor-phenoxyessigsäure3 2- {2-chlorophenylamidosulfonyl) - 162
4-chloro-phenoxyacetic acid

4 2-(4-Methylphenylamidosulfonyl)- 177
4-chlor-phenoxyessigsäure4 2- (4-methylphenylamidosulfonyl) - 177
4-chloro-phenoxyacetic acid

AusführungsbeispielEmbodiment

In einen mit Rührer, Thermometer und Tropftrichter versehenen 1-I-Kolben werden 500 g Chlorsulfonsäure auf 10 bis IS0C abgekühlt und im Laufe von 30 Minuten unter Rühren mit 100 g Methylester der p-Chlorphenoxyessigsäure versetzt. Die Temperatur wird sodann auf 600C erhöht und unter Rühren 1 Stunde lang beibehalten. Das Reaktionsgemisch wird abgekühlt und unter Rühren über eine Wasser-Eis-Mischung gegossen. Es fällt der Methylester der 2-Chlorsulfonyl-4-chlor-phenoxyessigsäure aus, welcher filtriert und mit kaltem Wasser gewaschen wird. Es werden 140 g Produkt mit dem Schmelzpunkt 74 bis 75 C erhalten. 500 g of chlorosulfonic acid are cooled to 10 to 15 ° C. in a 1-liter flask equipped with a stirrer, thermometer and dropping funnel, and 100 g of methyl ester of p-chlorophenoxyacetic acid are added over the course of 30 minutes while stirring. The temperature is then increased to 60 ° C. and maintained for 1 hour with stirring. The reaction mixture is cooled and poured over a water-ice mixture with stirring. The methyl ester of 2-chlorosulfonyl-4-chloro-phenoxyacetic acid precipitates, which is filtered and washed with cold water. 140 g of product with a melting point of 74 to 75 ° C. are obtained.

30 g des sulfochlorierten Esters werden in 60 ml30 g of the sulfochlorinated ester are in 60 ml

Aceton gelöst, 9 g Natriumbicarbonat zugegeben und sodann mit 12 g in 20 ml Aceton gelösten Metachloranilin behandelt.Dissolved acetone, added 9 g of sodium bicarbonate and then with 12 g of metachloroaniline dissolved in 20 ml of acetone treated.

Das Reaktionsgemisch wird auf 6O0C erwärmt, bis kein Kohlendioxyd mehr entweicht. Es wird dann abgekühlt und mit 500 ml Wasser behandelt. Beim Abkühlen kristallisiert der Methylester der 2-(m-Chlorphenyl-amidosulfonyl)-4-chlorphenoxyessigsäure aus, welcher filtriert wird (Schmelzpunkt = 1300C). AusThe reaction mixture is heated to 6O 0 C until no carbon dioxide escapes more. It is then cooled and treated with 500 ml of water. Upon cooling, the Methylester of 2- crystallized from (m-chlorophenyl-amidosulfonyl) -4-chlorophenoxy acetic acid, which is filtered (m.p. = 130 0 C). the end

4a dem Filtrat wird das Aceton zurückgewonnen.The acetone is recovered from the filtrate.

Das filtrierte Produkt wird durch 1 stündiges Sieden mit einer 4%igen Natriumhydroxydlösung der Hydrolyse unterworfen. Die Lösung wird mit Aktivkohle behandelt und mit Salzsäure auf einen pH-Wert von 2 angesäuert, worauf die 2-{m-Chlorphenylamidosulfo-The filtered product is hydrolysed by boiling for 1 hour with a 4% sodium hydroxide solution subject. The solution is treated with activated charcoal and adjusted to pH 2 with hydrochloric acid acidified, whereupon the 2- {m-chlorophenylamidosulfo-

nyi)-4-chlor-phenoxyessigsäure kristallisiert, welchenyi) -4-chloro-phenoxyacetic acid crystallizes, which

filtriert, mit Wasser gewaschen und getrocknet wird (Schmelzpunkt = 1830C). Die Ausbeute beträgt 70%.filtered, washed with water and dried (melting point = 183 0 C). The yield is 70%.

Die C, H, N, S-Analyse ergab folgende Werte:The C, H, N, S analysis resulted in the following values:

C 45,12%C 45.12%

H 3,05%H 3.05%

N 3,68%N 3.68%

S 8,36%S 8.36%

Bei den Produkten 1, 3 und 4 der Tabelle werden ähnliche Ausbeuten erhalten.Similar yields are obtained for products 1, 3 and 4 in the table.

Claims (5)

Patentansprüche:Patent claims: 1. 2 - (4 - Chlorphenylauiidosulfonyl) - 4 - chlorphenoxyessigsäure. 1. 2 - (4 - Chlorophenylauidosulfonyl) - 4 - chlorophenoxyacetic acid. 2. 2 - (3 - Chlorphenylamidosulfonyl) - 4 - chlorphenoxyessigsäure. 2. 2 - (3 - Chlorophenylamidosulfonyl) - 4 - chlorophenoxyacetic acid. 3. 2 - (2 - Chlorphenylamidosulfonyl) - 4 - chlorphenoxyessigsäure. 3. 2 - (2 - Chlorophenylamidosulfonyl) - 4 - chlorophenoxyacetic acid. 4. 2 - (4 - Methylphenylamidosulfonyl) - 4 - chlorphenoxyessigsäure. 4. 2 - (4 - methylphenylamidosulfonyl) - 4 - chlorophenoxyacetic acid. 5. Verfahren zur Herstellung der Verbindungen gemäß den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß man in an sich bekannter Weise Methylester der p-Chlorphenoxyessigsäure sulfochloriert, das Sulfochlorierungsprodukt mit einem entsprechenden aromatischen Amin kondensiert, das Reaktionsprodukt hydrolysiert und ansäuert.5. Process for the preparation of the compounds according to Claims 1 to 4, characterized in that that methyl ester of p-chlorophenoxyacetic acid is sulfochlorinated in a manner known per se, the sulfochlorination product condenses with a corresponding aromatic amine, the reaction product is hydrolyzed and acidified.
DE19722257148 1972-11-22 Phenylamidosulfonyl-phenoxy-acetic acids and process for their preparation Expired DE2257148C3 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19722257148 DE2257148C3 (en) 1972-11-22 Phenylamidosulfonyl-phenoxy-acetic acids and process for their preparation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19722257148 DE2257148C3 (en) 1972-11-22 Phenylamidosulfonyl-phenoxy-acetic acids and process for their preparation

Publications (3)

Publication Number Publication Date
DE2257148A1 DE2257148A1 (en) 1974-06-12
DE2257148B2 true DE2257148B2 (en) 1975-12-11
DE2257148C3 DE2257148C3 (en) 1976-07-15

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Publication number Publication date
DE2257148A1 (en) 1974-06-12

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