CS241550B2 - Process for the production of new 5-membered heterocyclic compounds - Google Patents

Abstract

The present invention relates to a process for the preparation of novel five-membered nitrogen-containing heterocyclic compounds which are used as active ingredients in insecticidal, acaricidal and nematicide compositions. French patent specification No. 2,315,422 (Chemical Abstracts CA 86; No. 106492c) discloses 1,2,3-oxathiazolidin-4-ones. However, nothing is known from this publication about the properties of these compounds as pest control agents. 1,2,3-oxazaphospholidine-2-oxides are known from J. Gen. Chem. USSR, vol. 43 I (1973), pp. 256 to 259. However, nothing is known about the properties of these compounds as pest control agents. It is also known that carbamates, such as 5,6-dimethyl-2-dimethylamino-4-pyrimidinyldimethylcarbamate or 1-naphthyl-N-methylcarbamate, have insecticidal activity (cf. U.S. Patent Nos. 3,493,574 and 2,903,478). However, the effect of these compounds is not always completely sufficient, especially at low applied concentrations. New five-membered nitrogen-containing heterocyclic compounds of the general formula I have now been found.

Description

The present invention relates to a process for the production of novel five-membered nitrogen-containing heterocyclic compounds which are used as active ingredients in insecticidal, acaricidal and nematicide compositions.

French Patent No. 2,315,422 (Chemical Abstracts CA 86; No. 106492c) discloses 1,2,3-oxathiazolidin-4-ones. However, nothing is known from this publication about the properties of these compounds as pest control agents. 1,2,3-oxazaphospholidine-2-oxides are known from J. Gen. Chem. USSR, Vol. 43 I (1973), pp. 256 to 259. However, nothing is known about the properties of these compounds as pest control agents.

Furthermore, carbamates, such as 5,6-dimethyl-2-dimethylamino-4-pyrimidinyldimethylcarbamate or 1-naphthyl-N-methylcarbamate, are known to have insecticidal activity (cf. U.S. Patent Nos. 3,493,574 and 2,903,478).

However, the effect of these compounds is not always completely sufficient, especially at low applied concentrations.

New five-membered nitrogen-containing heterocyclic compounds of the general formula I have now been found

R-N-^O (I) in which

X means group

SO, Si(alkyl)2, where alkyl contains 1 to 4 carbon atoms or a group

About \ll

PO(alkyl), %

where alkyl contains 1 to 4 carbon atoms,

R ¹ represents an alkyl group with 1 to 7 carbon atoms, or optionally an alkyl group with 1 to 4 carbon atoms and/or a phenyl group substituted by one or more identical or different halogen atoms,

R ^z represents a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 3 to 4 carbon atoms, an alkynyl group with 3 to 4 carbon atoms, optionally in the aryl part by one or more substituents from the group consisting of halogen, an alkyl group with 1 to 3 carbon atoms and a nitro group substituted by an aralkyl group with 7 to 11 carbon atoms, an acyl group with 2 to 4 carbon atoms, a benzoyl group which is optionally substituted in the phenyl part by halogen, an alkoxycarbonylmethyl group with 1 to 4 carbon atoms in the alkoxy part, an alkylcarbonylmethyl group with 1 to 4 carbon atoms in the alkyl part, an equivalent of an inorganic or organic cation or the groups SCCC13 and SCCI2F,

R ³ represents a group CONH 2 , CH 2 Cl, CCl 3 , an ethoxycarbonylmethyl group, a phenyloxymethyl group with 1 or more halogen atoms in the phenyl moiety, which have excellent pesticidal properties and can therefore be used as active ingredients of insecticidal, acaricidal and nematicide compositions.

The five-membered nitrogen-containing heterocyclic compounds of formula I occur in the form of mixtures of their spherical and optical isomers, as well as in the form of their pure isomers.

Czechoslovak patent specification No. 241,542 already describes some methods for preparing these new compounds of general formula I.

According to the present invention, compounds of the above-mentioned general formula I are prepared, in which

X means group \

Saturday /

or group

Si(alkyl)2Z where alkyl contains 1 to 4 carbon atoms,

R ¹ and R ³ have the meaning defined above and

R ² represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 3 to 4 carbon atoms, an alkynyl group with 3 to 4 carbon atoms, optionally in the aryl part by one or more substituents from the group consisting of halogen, an alkyl group with 1 to 3 carbon atoms and a nitro group substituted aralkyl group with 7 to 11 carbon atoms, an acyl group with 2 to 4 carbon atoms, a benzoyl group which is optionally substituted in the phenyl part by halogen, an alkoxycarbonylmethyl group with 1 to 4 carbon atoms in the alkoxy part, an alkylcarbonylmethyl group with 1 to 4 carbon atoms in the alkyl part, an equivalent of an inorganic or organic cation or the SCCI3 and SCCI2F groups, by applying to the compound of general formula IV (IV) in which

X, R ¹ and R ³ have the above meanings, act as a compound of general formula V

R ² —Z (V) in which

R ^z has the meaning given above and

Z represents a group that is reactive towards an acidic hydrogen atom.

The five-membered nitrogen-containing heterocyclic compounds produced by the process according to the invention surprisingly exhibit a significantly higher insecticidal activity than carbamates known from the prior art with the same type of activity, such as 5,6-dimethyl-2-dimethylamino-4-pyrimidinyldimethylcarbamate or 1-naphthyl-N-methylcarbamate (cf. U.S. Patent No. 3,493,574 and U.S. Patent No. 2,903,478).

In addition, new five-membered nitrogen-containing heterocyclic compounds exhibit favorable toxicity as well as systemic effect when taken up by plant roots.

Preferably, compounds of general formula I are prepared in which

R ¹ represents an alkyl group with 1 to 6 carbon atoms or a phenyl group which is optionally substituted by an alkyl group with 1 to 4 carbon atoms, in particular a methyl group and/or by one or more identical or different halogen atoms, in particular fluorine or chlorine atoms,

R ² represents an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 3 to 4 carbon atoms, an alkynyl group with 3 to 4 carbon atoms, an equivalent of cations from the group consisting of sodium, potassium, calcium, ammonium, trialkylammonium group with 1 to 4 carbon atoms in alkyls, morpholinyl,

R ³ represents a CONH 2 group, a CH 2 Cl group, a CCl 3 group, an ethoxycarbonylmethyl group, a phenyloxymethyl group with one or more halogen atoms in the phenyl moiety, and

X represents a group SO or

241350

Si(CH3)2 \

Other preferred compounds produced according to the invention are compounds of general formula I, wherein

R ¹ represents an alkyl group with 1 to 4 carbon atoms, in particular a methyl group, a tert-butyl group, a phenyl group, which is optionally substituted one to three times identically or differently by halogen, in particular fluorine, chlorine, bromine, iodine, an alkyl group with 1 to 4 carbon atoms, in particular a methyl group,

R ² represents sodium, an alkyl group with 1 to 4 carbon atoms, especially a methyl group, an ethyl group, an alkylcarbonyl group with 1 to 4 carbon atoms in the alkyl part, especially a methylcarbonyl group, an alkenyl group with 3 to 4 carbon atoms, especially an allyl group, an alkynyl group with 3 to 4 carbon atoms, especially a propargyl group,

R ³ represents a group CONH 2 , CH 2 O, CCl 3 , an ethoxycarbonylmethyl group, a phenyloxymethyl group with one or more halogen atoms in the phenyl part,

R ¹

X represents the group SO or Si(CH3)2.

It is particularly necessary to emphasize as advantageous the compounds of the general formula Ϊ, in which

R ¹ represents a tert-butyl group or a phenyl group which is optionally substituted one or more times with chlorine or a methyl group,

R ² represents sodium, methyl group, ethyl group, propargyl group, trichloromethylsulphenyl group, trialkylammonium group in which the alkyl radicals contain 1 to 4 carbon atoms, morpholinyl group,

R ³ represents the group GONH 2 , and

X has the meaning given above.

The following compounds of formula I can be listed separately:

R ²

ClctCH3

H2C=CH—CH2CHsCONa ⁺

CH3

C2H5

Ct

CH,

CH3SO2Na+

CONH2

CONH2

CONH2

CONH2

CONH2

CONH2

CONH2

CONH2

CONH2

SO so so so so so so so so (Ο2Η5)3ΝΗ· ⁾

C0NH2

SO

CH3

CONH2

SO

R ² R ³ ' X ^ct ^p- Ct C2H5 C0NH2 with Cl 11-C3H7 C0NH2 with ctxQ- Cl H2C=CH—CH2— C0NH2 with Cl HCeC—CH2— C0NH2 with ^ct -0- Cl CH3CO— C0NH2 with Cl CC13S— C0NH2 with Cl CFCI2S— C0NH2 with --Q- Cl 0-¾ C0NH2 with Cl-Q- Cl ct ct C0NH2 with ct ct Na+ C0NH2 with ct ct K CH3 C0NH2 with ct HC=C—CH2- C0NH2 with

R ¹

R ² R ³ X ci

Cl

Cl

(CH3)2CH- CONH2 SO CClsS— CONH2 SO CH3 CONH2 SO

The following compounds can also be mentioned:

R ³ ř?

R ¹ R ² R ³ t.butyl CH3 3.4-C12-C6H3OCH2- t.butyl C2H5 3,4-Cl2-CeH3OCH2— t.butyl C3H7 3,4-Cl2-CeH3OCH2-~ t.butyl n-GáHe 3,4-Cl2-C6H3OCH2— t.butyl Í-C3H7 3,4-Cl2-C6H3OCH2— t.butyl HC=C—CH>- 3,4-Cl2-C6H3OCH2— t.butyl H2C=CH—CH2— 3,4-Cl2-C6H3OCH2— t.butyl 3,4-Cl2-C6H3OCH2— t.butyl Cl 3,4-Cl2-C6H3OCH2— t.butyl Ct-ZO^-CH ₄ - Cl 3.4-C12-C6H3OCH2— t.butyl 4-Cl-CeH4OCH2— t.butyl Ci-ZO^-pH^ 4-C1-C6H4OCH2— t.butyl Í-G3H7 4-C1-C6H4QCH2- t.butyl n-C4H9 4-C1-C6H4OCH2— t.butyl C1 —-^Ó^— CR^ Cl 4-C1-C6H4OCH2—

R ^from

R’

4-Cl-CeH4—

4-C1-C6H4—

4-C1-C6H4—

4-C1-C6H4—

4-C1-C6H4—

4-C1-C6H4—

4-C1-C6H4—

4-C1-G6H4—

CHs

C2H5

11-C3H7

I-C3H7

HCsC—CH2— H2C=CH—CH2— n-C4H9

4-C1-C6H4—

4-C1-C8H4OCH2—

4-C1-C6H4OCH2—

4-C1-C8H4OCH2—

4-C1-C6H4OCH2—

4-C1-C6H4OCH2—

4-C1-C6H4OCH2—

4-Cl-CeH4OCH2—

4-C1-C6H4OCH2—

4-C1-C6H4OCH2—

Cl

4-C1-C6H4—

4-C1-C6H4—

4-C1-C6H4—

4-C1-C6H4—

4-C1-C6H4—

4-C1-C6H4—

4-C1-C6H4—

4-C1-C6H4—

3,4-Cl2-C6H3

3,4-Cl2-C6H3

3,4-Cl2-C6H3

3,4-Cl2-C6H3

3,4-Cl2-C6H3

3,4-Cl2-C6H3

3,4-Cl2-C6H3

CH3

C2H5

C3H7

I-C3H7 n-C4H9

H2C=CH—CH2 HC=C—CH2

CH3

C2H5

I1C3H7

I-C3H7

I1-C3H7

HC=C—CH2— H2C=CH—CH2—

3.4- Cl2-C6H3

3.4- C12-C6H3

3,4-Cl2-CeH3OCH2—

3.4- Cl2-CeH3OCH2—

3.4- Cl2-C6H3OCH2—

3.4- Cl2-C6H3OCH2—

3.4- C12-C6H3OCH2—

3.4- Cl2-CeH3OCH2—

3.4- Cl2-C6H3OCH2—

3,4-Cl2-C6H3OCH2—

4-C1-C6H4OCH2—

4-C1-C6H4OCH2—

4-G1-C6H4OCH2—

4-C1-C6H4OCH2—

4-C1-C6H4OCH2—

4-C1-C6H4OCH2—

4-C1-C6H4OCH2—

4-C1-C6H4OCH2—

3.4- C12-C6H3

3.4- Cl2-C6H3

3.4- CI2-C6H3

3.4- Cl2-C6H3

3.4- Cl2-C6H3

3.4- C12-C6H3

3.4- Cl2-C6H3

3,4-Cl2-C6H3

3,4-Cl2-C6H3—

4-C1-C6H4—

4-C1-C6H4—

4-C1-C6H44-C1-C6H4— ^cw /

Cl

CH3

C2H5

C3H7

1-C3H7

HCsC—CH2H2C=CH—CH2— n-C4H9 n-CeHi3

CH3

C2H5

HC=C—CH2— H2C=CH—CH2—

4-C1-C6H4OCH2—

3.4- Cl2-C6H3OCH2—

3.4- Cl2-CeH3OCH2—

3.4- C12-C6H3OCH2— '

3.4- Cl2-C6H3OCH2— 3,4-Cl2-C6H3OCH2—

3.4- Cl2-C6H3OCH2—

3.4- Cl2-C6H3OCH2~3.4- Cl2-C6H3OCH2—

3,4-Cl2-C6H3OCH2—

CONH2

CONH2

CONH2

CONH2

The reaction of compounds of formula IV with compounds of formula V according to the invention is optionally carried out in the presence of diluents and catalysts.

The process according to the invention can be illustrated, for example, by the following reaction scheme:

Η N ll

O

CONH _Z

Compounds of formula IV can be obtained by the process described in Czech patent specification No. 241,542 for the production of compounds of general formula I.

Compounds of formula V are known, examples of compounds of formula V include:

Alkylating agents, such as methyl bromide, methyl iodide, methyl chloride, ethyl bromide, ethyl chloride, ethyl iodide, 1-iodopropane, 2-iodopropane, allyl chloride, allyl bromide, propargyl bromide, propargyl chloride, benzyl chloride, benzyl bromide, 3,4-dichlorobenzyl chloride, dimethyl sulfate, diethyl sulfate. Acylating agents, such as benzoyl chloride, 3,4-dichlorobenzoyl chloride, 3chlorobenzoyl bromide, acetyl chloride, acetic anhydride, propionyl chloride, benzoyl cyanide, ethyl chloroformate, methyl chloroformate, methylsulfamoyl chloride, dimethylcarbamic chloride, phenyl chloroformate. Isocyanates, such as methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, dodecyl isocyanate, phenyl isocyanate, p-chlorobenzoyl isocyanate, o-chlorobenzoyl isocyanate, sulfonyl isocyanates, such as benzenesulfonyl isocyanate, 3,4-dichlorobenzoyl isocyanate.

Sulphenylating agents, such as trihalomethylsulfonic acid chloride, 2,3-trichloromethylsulfenic acid chloride, dichlorofluoromethylsulfenic acid chloride, trifluoromethylsulfenic acid chloride, chloride, optionally substituted phenylsulfenic acids, such as phenyl-, ρ-chlorophenyl-, p-trifluoromethylphenyl-, 3,4-dichlorophenylsulfenic acid chloride.

Sulfonylating agents, such as trimethylsilyl cyanide or trimethylsilyl chloride.

Sulfonating agents, such as tosyl chloride, phenylsulfonyl chloride, chlorophenylsulfonyl chloride.

Suitable diluents are all inert organic solvents. These include, in particular, aliphatic and aromatic, or halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, as well as ethers, such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, as well as ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, as well as esters, such as methyl acetate and ethyl acetate, as well as nitriles, such as acetonitrile and propionitrile, benzonitrile, glutaric acid dinitrile, as well as amides, such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, as well as dimethylsulfoxide, tetramethylenesulfone and phosphoric acid hexamethyltriamide.

Suitable acid-binding agents are all conventional acid-binding agents. These preferably include alkali metal carbonates, hydroxides or alkoxides, such as sodium or potassium carbonate, sodium or potassium hydroxide, sodium and potassium methoxide or ethoxide, and aliphatic, aromatic or heterocyclic amines, for example trimethylamine, triethylamine, tributylamine, dimethylaniline, dimethylbenzylamine and pyridine.

Compounds which are usually used as catalysts in reactions in two-phase systems consisting of water and water-immiscible organic solvents for the phase transfer of components (phase transfer catalysts) can be used. As such, tetraalkyl and trialkylaralkylammonium salts can be mentioned in particular, preferably with 1 to 10 carbon atoms, in particular with 1 to 8 carbon atoms in each alkyl group, preferably with phenyl as the aryl part of the aralkyl group and preferably with 1 to 4 carbon atoms, in particular with 1 or 2 carbon atoms in the alkyl part of the aralkyl groups. In particular, halides such as chlorides, bromides and iodides, preferably chlorides and bromides, are suitable. Examples include tetrabutylammonium bromide, benzyltriethylammonium chloride and methyltrioctylammonium chloride.

The reaction temperature is maintained between about 0°C and 130°C, preferably between about 20°C and 60°C. The process is preferably carried out at atmospheric pressure.

The reaction mixture is worked up in the usual manner.

The process according to the invention is illustrated in more detail by the following examples, which, however, do not limit the scope of the invention in any way.

Example 1

To a freshly prepared solution of 7 g of sodium methoxide in 200 ml of anhydrous methanol was added 40.2 g (0.13 mol) of 5-(3,4-dichlorophenyl)-5-aminocarbonyl-1,2,3-oxathiadiazolidin-4-one-2-oxide. After stirring for one hour at room temperature, the solvent was distilled off under reduced pressure, the remaining solid residue was triturated with diethyl ether and dried at room temperature.

This gives 43 g (100% of theory) of the sodium salt of 5-(3,4-dichlorophenyl)-5-aminocarbonyl-1,2,3-oxathiazolidin-4-one-2-oxide, which slowly decomposes at temperatures above 250°C with darkening.

The starting material can be prepared as follows.

144.5 g (0.55 mol) of 3,4-dichlorophenylhydroxymalonic acid diamide are suspended in 350 ml of thionyl chloride. The suspension is heated to boiling with stirring for 3 hours, then cooled to 10 °C and the precipitated crystals are filtered off. The crystals are washed with diethyl ether and dried at 50 °C.

This gives 120.5 g (70.9% of theory) of 5-(3,4-dichlorophenyl)-5-aminocarbonyl-1,2,3-oxathiazolidine-4-one-2-oxide in the form of slightly yellowish crystals which melt with decomposition at a temperature between 191 and 192 °C.

Example 2

To a solution of 6.2 g (0.02 mol) of 5-(3,4-dichlorophenyl)-5-aminocarbonyl-1,2,3-oxathiazolidin-4-one-2-oxide and 2.02 g (0.02 mol) of triethylamine in 50 ml of acetonitrile is added 31.2 g (0.2 mol) of ethyl iodide. The solution obtained is heated to boiling for 4 hours and then evaporated under reduced pressure. The residue is taken up in 50 ml of dichloromethane and washed three times with 20 ml of water each time. The organic phase is evaporated and the residue is triturated with diethyl ether. Thus -dichlorophenyl)-5-aminocarbonyl-1,2,3-oxathiazolidin-4-one-2-oxide with a melting point of 112 to 128 °C.

By an analogous procedure to that described in Examples 1 and 2, the following compounds of the general formula Γ are prepared:

O=y—jR ² · ř/1 example.

number

R ²

R ³

CH3

SCC12

C0NH2

CONHž

CONHž.

C0NH2 physical properties

mp 173 to 173.5 °C viscous oil]

m.p. 174 °C

C2H5

CH3

C2H5

CH2-—CH—CH2 —CH(CH3)2

CH3

CONH2

CONH2

CON-Hr

CONH2

CONH

CONH2

CONH2

CONH2 tert.C4H9 tert.C4H9

m.p. 135 °C (decomposition)

m.p. 174 °C

1.1; iW' ^o er

t. t. llWaž117 °C

1.1.136 to 138°C

mp 161 to 163 °C tí tí.lTBW 168PG'

tp 260 °C n _D ²⁰ 1.5330

Πύ ²⁰ ' 1.5280 example number

R ²

R ³ physical physical

CH2—C=CH

CH3

-ch _£ o ~ ^CH Z° ~C _Hi O

-CH.0

C.

C2H5 _CH2—C=CH tert.C4H9 tert.C4H9 tert.C4H9 tert.C4H9 n _D ²⁰ 1.5404

mp 110 to 116 °C

mp 101 to 104 °C

mp 102 to 104 °C

tert.C4H9 tert.C4H9

mp 107 to 108 °C

mp 91 to 92 °C

The compounds shown in the following examples are also prepared by an analogous procedure:

Physical data:

melting point 109 to 114°C (from ethanol).

Analysis for:

C20H20Cl3NO4S (molecular weight 476.6)

Example 24 %2Vch ₄ °-< ^o :

Cl

Example 25 about Cl

CH ₂ N' _S '° ci o

Physical data:

melting point 126 to 132°C (from ethanol)

Analysis for:

C20H20Cl2N2O6 (molecular weight 487.1) Example 26

Physical data:

melting point 148 to 152 °C (from ethanol)

Analysis for:

C20H20Cl2N2O6 (molecular weight 487.1)

Physical data: resin

Analysis for:

C20H20Cl3NO4S (molecular weight 476.6)

Example 27

Example 31

Whose

IC^C-CH/Mxs g

O

Physical data:

melting point 123 to 127°C (from ethanol)

Analysis for:

C20H20Cl2N2O6 (molecular weight 487.1)

Example 28

Cí ,CH _? O

O _? NO >- C H-rŇv'° Cí

Physical data: melting point 94 to 95 °C

Analysis for:

C16H2ClNO3S (molecular weight 355.8) Example 32 °y^' ^CH 2 ⁰ ^2X ^Ct

HC=C“CHrNv _S -0

Physical data: resin

Analysis for:

C20H20Cl2N2O6 (molecular weight 487.1]

Example 29

Ov 0--<O)-a

£.

Ci . Cl o

Physical data: viscous oil

Analysis for:

C17H19Cl4NO4S (molecular weight 475.0)

Example 30

Physical data: melting point 103 to 104 °C

Analysis for:

C16H18CINO4S (molecular weight 355.8)

Physical data:

melting point 137 to 140 °C (from ethanol)

Analysis for:

C20H19Cl4NO4S (molecular weight 511.3)

34 ct.

Whose

O.

y-r

CH£N-s'° ^cí

Whose

Physical data:

melting point 109 to 111 °C (from ethanol)

Analysis for:

C20H19Cl4NO4S (molecular weight 511.3)

Physical data: viscous oil

Analysis for:

C19H23C14NO4S (molecular weight 503.0)

Example 35

O

Analysis for:

C20H19NO4S4 (molecular weight 511.3) Example 39

Physical data:

melting point 109 to 113 °C (from ethanol)

Analysis for:

C20H20Cl3NO4S (molecular weight 476.6)

Physical data: brittle resin

Example 36

Ct,

Analysis for:

C24H27Cl2NO4S (molecular weight 496.2)

CH^N

CK0-<0

Example 40

Physical data: resin ct s

O

O

O

Physical data: brittle resin

Analysis for: C20H20Cl3NO4S

Analysis for:

C24H27Cl2NO4S (molecular weight 496.2)

Physical data:

melting point 97 to 103 °C (from ethanol)

Analysis for:

C20H19Cl4NO4S (molecular weight 511.3)

Example 38

Example 41

Physical data:

ct ct

Analysis for:

C24H23Cl2NO4S (molecular weight 492.2)

Example 42

Physical data:

melting point 128 to 132 °C (from ethanol)

Analysis for: C24H23Cl2NO4S

Example 43

CHjN^O

O

Ct

Analysis for:

C19H25Cl2NO4S (molecular weight 450.1)

Example 44

Analysis for:

C19H25Cl2NO4S (molecular weight 450.1)

Physical data: viscous oil, n _D ²⁵ 1.5381

Analysis for:

C14H17Cl2NO4S (molecular weight 366.3)

Example 48

Example 45

WHOSE

HCsC-CH^N

O

Physical data: viscous oil, n _D ²⁵ 1.5424

Analysis for:

C16H17C12NO4S (molecular weight 390.3j

Example 46

Physical data: viscous oil, n _D ²⁵ 1.5374 ct

Physical data: viscous oil, n _D ²⁵ 1.5318

Analysis for:

C15H19Cl2NO4S (molecular weight 380.3] Example 49

Physical data: viscous oil, n _D ²⁵ 1.5 3 30

Analysis for:

Analysis for:

C16H19Cl2NO4S (molecular weight 392.3)

C16H21Cl2NO4S (molecular weight 394.1)

Example 54

0.

,CH^O-\O/-Cl

Physical data: waxy product

Analysis for:

C16H21Cl2NO4S (molecular weight 394.1) Example 51

C^-N-s Ό Cl

Physical data: viscous oil, n _D ²⁵ 1.5318

Analysis for:

C17H23Cl2NO4S (molecular weight 408.1) Example 55

Cl

A-»/ Ύ OCa \XW/

C ₅ Hj]M- _s -° ' CHICI

Physical data: viscous oil

Analysis for:

CI8H25CI2NO4S (molecular weight 422.1) Example 52

Cl·

Physical data: viscous oil, n _D ²⁵ 1.5262

Analysis for:

C17H23Cl2NO4S (molecular weight 408.1) Example 56

Cl .CH^O-^^-Cl _h -CH=CW-CH£N-s' ⁰

Physical data: viscous oil

Analysis for:

C18H25C12NO4S (molecular weight 422.1) Example 53

Physical data: viscous oil, n _D ²⁵ 1.5423

Analysis for:

C17H21Cl2NO4S (molecular weight 406.1)

Example 57

Physical data:

viscous oil, n _D ²⁵ 1.5348

Physical data: viscous oil, n _D ²⁵ 1.5372

Analysis for:

C15H17Cl2NO5S (molecular weight 394.1)

241350

Analysis for:

C17H21C12NO4S (molecular weight 406.1)

Example 58

CH^O % ⁰

Physical data: viscous oil, n _D ²⁵ 1.5398

Analysis for:

C17H21CI2NO4S (molecular weight 406.1 J

Example 59

Analysis for:

C20H19Cl2NO5S (molecular weight 456.1) Example 62

CH^-N^O o

Ci cC

Physical data:

viscous oil, n _D ²⁵ 1.5 3 9 2

Analysis for:

C17H20Cl3NO4S (molecular weight 440.6j Example 63

Physical data: viscous oil, n _D ²⁵ 1.5338

Physical data: viscous oil. n _D ²⁵ 1.5282

Analysis for:

Cl7H2lCl2NO4S (molecular weight 406.1 J

Analysis for:

C19H24Cl3NO4S (molecular weight 468.6 j

Example 60

H^C^C-CHf N*s° Ct O

Analysis for:

C16H19Cl2NO4S (molecular weight 392.3J

Example 61

Physical data:

viscous oil, n _D ²⁵ 1.5519

Analysis for:

C16H18Cl3NO4S (molecular weight 426.5J Example 65

Physical data:

melting point 133 to 138 °C (from ethanol)

Physical data:

viscous oil, n _D ²⁵ 1.5442

Analysis for:

C16H18C13NO4S (molecular weight 426.5J

Example 66

Physical data: melting point 160 to 165 °C

Analysis for:

C20H18Cl2N2O6S (molecular weight 487.1] Example 70

O

Physical data:

melting point 107 to 110°C (from ethanol)

Analysis for:

C21H23Cl2NO4S (molecular weight 456.1)

Example 67

Cl

Physical data:

melting point 133 to 134°C (from ethanol)

Analysis for:

C20H20CINO5S (molecular weight 421.7)

CiO

Physical data:

viscous oil, n _n ²⁵ 1.5 5 80

Physical data:

melting point 119 to 122 °C (from ethanol)

Analysis for:

C21H23Cl2NO4S (molecular weight 456.1]

Analysis for:

C20H21CIN2O6S (molecular weight 452.7)

Example 68

CV

Physical data: melting point 137 to 141 °C

Physical data:

melting point 148 to 158°C (from ethanol)

Analysis for: C15H17CI2NO5

Analysis for:

C20H20Cl2N2O6S (molecular weight 487.1)

Example 73

Analysis for:

CI6H19CI2NO4S (molecular weight 392.1)

Analysis for:

C24H24C1NO4S (molecular weight 469.7)

Example 74

^Whose

O

Example 78

O/-Cl ''Cl

Physical data: resin

Analysis for:

C24H24C1NO4S (molecular weight 492.2]

Physical data: viscous oil, n _D ²⁵ 1.5515

Analysis for:

C16H12CbNO6S (molecular weight 426.5) Example 79

Example 75

₀ ^ch 3 O

Physical data: viscous oil, n _D ²⁵ 1.5379

Physical data: viscous oil, n _D ²⁵ , 1.5400

Analysis for:

C17H21Cl2NO4S (molecular weight 406.1] Example 76

Physical data: viscous oil

Analysis for:

CI6H19CI2NO6S (molecular weight 424.1]

Analysis for:

C15H18CINO5S (molecular weight 359.6)

Physical data: viscous oil, n _D ²⁵ 1.5485

Analysis for:

C15H17Cl2NO5S (molecular weight 394.1) Example 81

O

Physical data: waxy product

Example 77

CH ₂ =C-CH^Nx _with .O

Cl o

Physical data:

viscous oil, n _D ²⁵ 1.5421

Analysis for:

C19H26CINO5S (molecular weight 415.7) Example 82

Physical data: viscous oil

Analysis for:

C17H22FNO6S (molecular weight 387.2)

Example 86

O=C

O {CH ₃ ) ₅

Physical data: viscous oil

Analysis for:

C19H25Cl2NO5S (molecular weight 450.1)

Example 83

Physical data: melting point 106—108 °C

Analysis for:

C20H21FN2O6S (molecular weight 436.2)

N

CH,

CHx-\ O

22^ c^o /0^ 'S'° o

Cl.

Physical data:

melting point 120—125 °C (from ethanol)

Analysis for:

C21H24CINO4S (molecular weight 421.7)

Physical data: melting point 110—115 °C

Analysis for:

C20H21FN2O6S (molecular weight 436.2)

Example 88

Example 84

o.. A-Oco/OV ·· CÍCH

³ \_r

Cl

CH, Oý-CH^N-s-O O

Physical data:

melting point 121—123 °C (from ethanol)

Analysis for:

C21H23Cl2NO4S (molecular weight 456.1)

Physical data:

melting point 126—128 °C

Analysis for:

C21H24FNO4S (molecular weight 405.5)

Example 89

Example 85 about -@- ^F

N^s<°

C^H ₅ OOC~CH^ o

Physical data:

viscous oil

Analysis for:

C16H22FNO4S (molecular weight 343.4)

Analysis for:

C19H26FNO5S (molecular weight 399.2)

Example 90

Example 94

^C S ^H ,í ^N 'S-° o

Physical data: viscous oil

Analysis for:

C24H22FNO4S (molecular weight 441.3) Example 91

Physical data: viscous oil

Analysis for:

C18H26FNO4S (molecular weight 371.5)

CC

^oh and

Physical data: viscous oil

Physical data: viscous oil

Analysis for:

C15H18FNO5S (molecular weight 343.2] Example 92

C H.~ C~C

Cl o

Analysis for:

C18H25Cl2NO4S (molecular weight 422.4) Example 96

O

Physical data: viscous oil

Physical data: viscous oil

Analysis for: C16H19CIFNO4S

Example 93

Analysis for:

C17H24FNO4S (molecular weight 357.5) Example 97

O

Physical data:

viscous oil

Physical data:

viscous oil

Analysis for:

C17H21CI2NO4S (molecular weight 406.3)

Example 98

CH _r CH=CW-CW/N^-0 o

Analysis for:

C17H22FNO4S (molecular weight 355.2)

Example 102

Whose

Physical data: melting point 163—166 °C

Example 99

O

Analysis for:

C20H19CIFNO5S (molecular weight-439.7)

Example 103

CW,= C-CH/N>S'° i j A

CH,

Physical data: viscous oil

Analysis for:

C17H22FNO4S (molecular weight 355.2) Example 100

Physical data: viscous oil

Analysis for:

C14H18FNO4S (molecular weight 315.2)

_people

O

CHjOOC-CH^-Ç^x ⁰ O

Physical data: viscous oil

OH

Example 104

C^s^s- ⁰

O

Analysis for:

C16H20FNO6S (molecular weight 373.2)

Example 101

O

Physical data:

melting point 99—103°C (from ethanol)

Analysis for:

C20H20Cl2FNO4S (molecular weight 460.1)

Physical data: viscous oil

Analysis for:

C15H20FNO4S (molecular weight 329.2) Example 105

HCsC-CH£MS' ⁰

O

Physical data:

viscous oil

Analysis for:

CieHieFNCUS

Example 110

Cl

Physical data:

melting point 112—116 °C (from ethanol)

Physical data:

melting point 107—110 °C (from ethanol)

Analysis for:

C20H22FNO4S (molecular weight 391.2)

Example 107

Analysis for:

C20H21CIN2O6S (molecular weight 452.9) Example 111

r

CH£)

(CH^CH-N^O

About

^CH F ^N ''

Analysis for:

C16H21Cl2NCUS (molecular weight 394.3)

Example 108

Cl

Physical data: viscous oil

Analysis for:

C24H28C1NO4S (molecular weight 462.0) Example 112

O

Cí ‘CtPhysical data: melting point 125—130 °C

Analysis for:

C20H19Cl4NO4S (molecular weight 511.3) Example 109

Physical data:

melting point 117—118 °C (from ethanol)

Analysis for:

C'20H20Cl3NO4S (molecular weight 476.8) Example 113

Cl· o

Whose

Physical data:

melting point 73—76 °C (from methanol)

Physical data:

melting point 112—114°C (from ethanol)

Analysis for:

C20H21CIFNO4S (molecular weight 425.9)

Analysis for:

C20H20Cl3NO4S (molecular weight 476.8)

Example 118

Physical data: melting point 128—132 °C

Cl

ct ct

CHj(CHí,q ^CH i ^N

(from ethanol)

Analysis for:

C20H19Cl4NO4S (molecular weight 511.3)

Example 115

what about

O>-F ^CH Í ^N 'S^° Ct o

Physical data: viscous oil

Analysis for:

C18H26CINO4S (molecular weight 387.7)

Example 119

Ο.η X/CÍ ^c Xs'^S' ⁰ o

Physical data:

melting point 103—107 °C (from ethanol)

Analysis for:

C20H20Cl2FNO4S (molecular weight 460.1)

Physical data: viscous oil

Analysis for: C17H24CINO4S

Example 120

Example 116

CH^C-CH^N^'O

O

Physical data: melting point 81—86 °C

Analysis for:

C20H21CIFNO4S (molecular weight 425.9)

Physical data: viscous oil

Analysis for: C17H22CINO4S

Example 121

Example 117

CHjCHzCH-CH^N^O

O

Physical data: viscous oil

Analysis for:

C17H22CINO4S

CHjOOC-CH^-N.s' ⁰ o

Physical data:

melting point 58—68 °C (from ethanol)

Analysis for:

G16H20CINO6S (molecular weight 389.6)

Example 122 Example 126

Physical data: viscous oil

Analysis for:

C17H22CINO6S (molecular weight 403.9) Example 123

Physical data: melting point 171—174 °C

Analysis for: C20H16Cl3NO5S

Example 124

Cl

Physical data: melting point 127 to 128 °C

Analysis for:

C20H18Cl2FNO5S (molecular weight 474.3)

Example 125

Physical data:

melting point 76 to 78 °C (from ethanol)

Analysis for:

C20H21Cl2NO4S (molecular weight 442.1)

Physical data:

melting point 98 to 100°C (from ethanol)

Analysis for:

C&0H20Cl3NO4S (molecular weight 476.6) Example 127

CH=CH -CH£t^5'° * O

Physical data: viscous oil, no ²⁰ 1.5365

Analysis for:

C16H20CINO4S (molecular weight 357.8) Example 128 ⁰ y^ ^c «> ⁰ -<O

CHfCH-CHfN^O

O

Physical data: viscous oil

Analysis for:

CI6H20FNO4S (molecular weight 341.4) Example 129

O

Physical data: melting point 167 to 172 °C

Analysis for:

C20H19Cl2NO5S (molecular weight 456.1)

Example 130

Example 134

CH,

XX ct

CH

Physical data: viscous oil

Analysis for:

C16H22CINO4S (molecular weight 359.6)

Physical data: melting point 107 to 108 °C

Analysis for:

C20H21Cl2NO4S (molecular weight 378.4)

Example 135

Example 131

Physical data: viscous oil

Physical data: viscous oil

Analysis for: C16H19CI2NO4S

Example 132

O

Physical data:

melting point 91 to 92 °C

Analysis for:

C20H22CINO4S (molecular weight 407.8j

Example 133

Analysis for:

C15H19Cl2NO4S (molecular weight 380.3) Example 136

O

Physical data: viscous oil

Analysis for:

C14HKCl2NO4S (molecular weight 366.3)

HC^C-CH ₂ N>S'°

O

Physical data: viscous oil

Analysis for:

G16H17CI2NO1S (molecular weight 390.3)

Example 137

CH^O

>-CH _z -K _s X) 'Ct ⁰

Physical data:

melting point 99 to 102°C (from ethanol)

Analysis for:

C20H20Cl3NO4S (molecular weight 476.6)

Example 138

Example 142

-/oV cp cp

Physical data:

melting point 88 to 90 °C (from ethanol)

Analysis for:

G20H21Cl2NO4S (molecular weight 442.1) Example 139

About -<£>-»

Physical data: melting point 110 to 116 °C

Analysis for:

C14H17Cl2NO4S

Physical data: melting point 101 to 104 °C

Physical data: n _D ^Z0 1.5330

Analysis for: C15H19CI2NO4S

Analysis for: C14H18CINO4S

Example 144

Physical data: no ²⁰ 1.5280

Analysis for: C15H20CINO4S

Example 141

HC2C-CH2N2S' ⁰

Q °·γΞγ^ ₄ 0-(O/Ct

HCsC-CH£Nx _S -0 O

Physical data: melting point 101 to 104 °C

Analysis for:

C16H17Cl2NO4S

Example 145

Physical data: melting point 85 to 89 °C

Analysis for: CieHuClNChS

Physical data: melting point 120 to 121 °C

Analysis for:

C12H10Cl2N2O4S (molecular weight 349.2)

241350

Claims (1)

OBJECT OF THE INVENTION A process for the preparation of the novel five-membered heterocyclic compounds of formula (I) 0 = 1 - + - R ⁵ , / ^N r ° R ii) in which X represents a carbon atom, a C2 -C4 acyl group, a benzoyl group optionally substituted in the phenyl moiety by halogen, an alkoxycarbonylmethyl group having 1 to 4 carbon atoms in the alkoxy moiety, an alkylcarbonylmethyl group having 1 to 4 carbon atoms in the alkyl moiety , an equivalent of an inorganic or organic cation or group SCC13 and SCCI2F, R ³ represents CONH 2, CH 2 Cl, CC13, ethoxycarbonylmethyl, fenyloxymethylovou group having one or more halogen atoms in the phenyl part, characterized in that the compound of formula IV or 0becného group \ I z ' SO Si (alkyl) 2 *-Χ ' ^O • R * (IV) wherein alkyl contains 1 to 4 carbon atoms, R ¹ represents an alkyl group having 1 to 7 carbon atoms or optionally an alkyl group having 1 to 4 carbon atoms and / or one or more, the same or different halogen atoms, a substituted phenyl group, R ² represents an alkyl group having 1-5 carbon atoms, alkenyl having 3-4 carbon atoms, alkynyl with 3-4 carbon atoms, optionally in the aryl moiety by one or more substituents selected from the group consisting of halogen, alkyl having 1-3 carbon and an aryl substituted aralkyl group having from 7 to 11 carbon atoms; X, R ¹ and R ³ are as defined above, with a compound of formula V wherein R ² -Z (V) R ² has the abovementioned meaning and Z represents a group which is reactive to the acidic hydrogen atom.