DD270910A1 - PROCESS FOR PREPARING NOVEL 3,3-PENTAMETHYLENE-1,2,4-THIADIAZOLIDINES - Google Patents

Abstract

The invention relates to a process for the preparation of novel 4-substituted-5-methylene-3,3-pentamethylene-1,2,4-thiadiazolidinen by reacting corresponding ketene S, N-acetals with 3,3-Pentamethylenoxaziridin, in the middle to good yields and with the simplest technological steps (reaction at room temperature, isolation of the products by crystallization) is feasible. The invention can be used for the production of biologically active agents and in the rubber industry.

Description

NHR *

in the

R ¹ , R ² and R ^{3 have} the meaning given for the formula I and R ^{4 is} hydrogen or a metal,

in powdered or dissolved form with a solution of 0.8 to 3 mol of 3,3-Pentamethylenoxaziridin reacted at temperatures from -70 to +110 ⁰ C and the reaction product I by crystallization, optionally after concentration of the reaction solution and addition of further solvents, is isolated ,

2. The method according to claim 1, characterized in that the ketene S, N-acetal II is dissolved in dimethylformamide or in dilute sodium hydroxide solution or its salt in water.

3. The method according to claim 1 and 2, characterized in that is reacted with 1.0 to 1.8 mol of 3,3-Pentamethylenoxaziridin.

4. The method according to claim 1 to 3, characterized in that the 3,3-Pentamethylenoxaziridin is used in toluene solution.

5. The method according to claim 1 to 4, characterized in that the reaction takes place at temperatures between 0 and +60 ⁰ C.

6. The method according to claim 1 to 5, characterized in that the reaction is started at room temperature.

7. The method according to claim 1 to 6, characterized in that the reaction of a solution of the ketene-S, N-acetal II is carried out under cooling with the oxaziridine solution so that the temperature of 40 to 60 ⁰ C is not exceeded.

Field of application of the invention

The invention relates to a process for the preparation of novel 4-substituted-5-methylene-3,3-pentamethylene-1,2,4-thiadiazolidinen, which are useful as intermediates for further syntheses or components of biologically active formulations due to their fungicidal activity or adjuvants for the Rubber industry, as a regulator of vulcanization speed, are used.

-2- 270 Characteristic of the known state of the art

Technical solutions which are close to the object of the present invention have hitherto not been known. All the compounds obtained by the process according to the invention are novel.

Object of the invention It is an object of the invention to develop a rational process for the preparation of 3,3-pentamethylene-1,2,4-thiadiazolidines. Explanation of the essence of the invention

The object of the invention is achieved by a process for preparing novel 3,3-pentamethylene-1,2,4-thiadiazolidines of general formula I,

in the mean

R ¹ , R ² H, COOR (R = alkyl or aryl), CN, acyl, wherein R ¹ and R ² together can also form a common ring and R ^{3 is} aryl or alkyl, which may optionally also be substituted,

according to the invention a ketene S, N-acetal or its salt of general formula II,

NHRT

in the

R ¹ , R ² and R ^{3 have} the meaning given for the formula I and R ^{4 is} H or a metal, for example the alkali metal Na,

in powdered or dissolved form with a solution of 0.8 to 3 mol, preferably 1 to 1.8 mol, 3,3-Pentamethylenoxaziridinbei temperatures of -70 to +110 ⁰ C, preferably 0 to + 6O ⁰ C, urret. The reaction is up in a few minutes

a maximum of 4 hours, which can easily be monitored by thin-layer chromatography. Depending on the batch size, a '

Heating the reaction mixture, which may be limited by cooling if necessary. The products are isolated by suction if they are immediately crystalline or after concentrating Reaction solutions, if appropriate after addition of gasoline, ether or an Aikohol / water mixture. The products are I

stable, colorless to yellow substances that oxidize 2 equivalents of potassium iodide to iodine.

The following examples serve to illustrate the invention. In some cases, in animal usually when using alkali salts

of II, by-products are isolable.

embodiments example 1

5 - / (cyano) (ethoxycarbonyl) methylidene / -3,3-pentamethylene-4-phenyl, 2,4-thiadiazolidine (I: R '= CN, R ² = EtOOC, R ³ = Ph)

2.5 g (10 mmol) of phenylamino-mercapto-cyano-ethoxycarbonyl-ethylene are dissolved in a little toluene and treated with 1 mmol of 3,3-pentamethoxy-oxaziridine in toluene After standing for 3 hours at room temperature, the volume is reduced to Va under reduced pressure , after careful addition of ether and gasoline the

Titelverbindur.g fails. Yield: 2.2 g (64% of theory), mp 140 to 142 ⁰ C (ausToluen / Benzln).. Example 2

5 - / (cyano) (ethoxycarbonyl) methylidene / -3,3-pentamethylene-4-phenyl-1,2,4-thiadiazolidine (1: R ¹ = CN, R ² = EtOOC ₁ R ³ = Ph) 6.76g (26 mmol) (phenylamino-sodium mercapto-cyano-ethoxycarbonyl-ethylene are dissolved in a little water and stirred vigorously with a 39 mmol 3,3-pentamethylene-oxaziridine solution in toluene After 2.5 hours, the phases are separated and the toluene phase is added as worked up in Example 1.

Yield: 3.6 to E, 1 g (40 to 67% of theory). After acidification of the aqueous phase with conc. HCI fall 1.4 to 1.7 g (23 to 28% of theory) (HydroxYMphenylamlno) -2-cyano-2

Ethoxycarbonyi-ethylene, mp. 133 to 135 ⁰ C (from nf-rOH).

Example 3 B- (DicYanrr.athYliden) -3,3-pentamethylene-4-phthalim .domethYl ^l-1 _l 2,4-thiadiazolldin (l: R \ R ⁱ "CN ₁ R ^3" Phthalimldomethyl)

2.8 g (AO mmol) (mercapto) (phthalimidomethyl) * 2,2-dicyanoethylene are stirred for 3 hours in a Ί6mmol containing

After standing overnight, a cloud is passed through and underflow

Concentrated pressure to about ¹ A volume. The precipitated after the addition of ether crystals are filtered off with suction and with ether

washed.

. Yield: 2.83 g (75% of theory), pale yellow crystals, mp 146-147 ⁰ C (ausToluan). Example 4

e-t-dicyan-methylidene-SS-pentamethylene ^ -phenYl-i ^^ - thladlazolidine-.R'.R * "CN, R ³ " Ph)

2.0 g (10 mmol) of (MeruApto) (pheny'amino) -2,2-dcyanothyiene 1.55 s (52% of theory) of the title compound are obtained analogously to Example 3

as pale yellow crystals, mp. 136 to 138 ⁰ C (from benzene / toluene).

When using the sodium salt of the starting compound is obtained only minimal amounts of the target product. example

6- (ethoxycarbonylmethylidene) -3,3-pentamethyl-4-phenyl-1,2,4-thiadiBZOlidtn (I-.R ¹ = H ₁ R ² = EtOOC, R ³ "Ph) 3.2g (10mmol) sodium salt of (MercaptoHphenylamlno ^ -othoxycarbonylethylenes give, analogously to Example 2, exactly 1.1 g (35% of theory) of the title compound, mp 168 to 17O ⁰ C (from EtOlI).

Examples S-di-tethoxycarbonyDmethyllden-SS-pentamethylene -phenyl ^ '.- i ^^ - thiadlazolldlnlhR ¹ x ^{1' 1} = R ₁ ³ EtOOC "Ph)

6.8 g (23 mmol) of (mercapto-phenylamino) -2,2-di- (ethoxycartone-anyD-ethylene give, analogously to Example 1, exactly 3.7 g (54% of theory) of

Titelverblndung, mp. 16O ⁰ C (from EtOM). A precipitate present after the reaction is filtered off before concentrating the toluene solution. He consists of the Sulfenamide (EtOOOjC = C (NHPh) SNH ,, yield to ιθ% of theory, mp.189 to 190 ^e C. Example 7

5- (4 ₁ 4-Dlmethyl-2, e-dioxo-3,6-dioxacYclohexyliden) -3,3-pentamethylene-4-phenyl-1,2,4-thiadiazolldin (UR ^1, R ¹ = -CO-O -CMey-O-CO-, R ³ = Ph)

2.8 g (10 mmol) of (4,4-dimethYl-2,6-dioxo-3,5-dioxacyclohexylidene) (mercapto) -N-phenyl-lmomethane are stirred with about 15 mmol of 3,3-pentamethylene-oxaziridine in toluene, until virtually no starting material can be detected by thin-layer chromatography is. This requires 2 to 4 hours at room temperature. 2.4 to 2.7 g of the target product can be suctioned off, another 0.2 to 0.6 g are obtained after concentration of the mother liquor and addition of ether.

. Yield: 2.6 to 3.2 g (66 to 82% of theory), mp 168 ⁰ C (from dioxane).

Claims (1)

i J claims: 1. A process for the preparation of novel 3,3-pentamethylene-1,2,4-thladiazolidines of the general formula I, in the R ¹ and R ² , which may be the same or different, are hydrogen, COOR (R = alkyl or aryl), CN and acyl, or R ¹ and R ² together form a ring and R ^{3 represents} an aryl or alkyl radical which may optionally also be substituted, characterized in that a ketene-S, N-acetal or its salt of the general formula II