CS241550B2 - Method of new quintuple-effect heterocyclic compounds production - Google Patents

Abstract

The present invention relates to a method of manufacture new 5-membered heterocyclic nitrogen-containing compounds to be used as active ingredients of insecticidal, acaricidal and nematocidal agents. From the French Patent Specification Number 2 315 422 (Chemical Abstracts CA 86; no 106492c) 1,2,3-oxathiazolidine-4- -they. However, nothing is known from this publication about the properties of these compounds as compositions to control pests. 1,2,3-oxazaphospholidine-2-oxides are known from J. Gen. Chem. USSR, vol. 43 I (1973), pp. 256-259 of these compounds as compositions however, pest control is not known. Furthermore, it is known that carbamates such as 5,6-dimethyl-2-dimethylamino-4-pyrimidinyldimethylcarbamate or 1-naphthyl-N-methylcarbamate, have insecticidal activity (cf. No. 3,493,574 and U.S. Pat 2,903,478 j. However, the effect of these compounds is not always especially at low applied concentrations quite sufficient. New five-membered heterocyclic compounds have now been found compounds containing nitrogen of Formula I

Description

The present invention relates to a process for the preparation of novel five-membered nitrogen-containing heterocyclic compounds which are used as active ingredients of insecticidal, acaricidal and nematicidal 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-oxazaphospholidin-2-oxides are known from J. Gen. Chem. USSR, Vol. 43 I (1973), pp. 256-259. 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 action of these compounds is not always sufficient, especially at low applied concentrations.

We have now found new five-membered nitrogen-containing heterocyclic compounds of formula I

R-N- (O) wherein

X is a group

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

O \ ll

PO (alkyl),%

wherein the 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 ^z is hydrogen, alkyl of 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 of 1 (C až-C ar) -alkyl, (C až-C ar ac) acyl group, (C až-C ac ac) acyl group, benzoyl optionally substituted in the phenyl by halogen, (C až-C alko alko) alkoxycarbonylmethyl, alkylcarbonylmethyl (C 1 -C 4) alkyl moiety, equivalent of inorganic or organic cations, or SCCl 3 and SCCl 2 F;

R ³ represents CONH 2, CH 2 Cl, CC13, ethoxycarbonylmethyl, fenyloxymethylovou group having one or more halogen atoms in the phenyl part, which have excellent pesticidal properties, and can therefore be used as active ingredients of insecticidal, acaricidal and nematocidal agents.

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

In MS. U.S. Pat. No. 241,542 already discloses some processes for the preparation of these novel compounds of formula (I).

According to the present invention, compounds of formula (I) above are prepared wherein:

X stands for \

SO /

or a group

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

R ¹ and R ³ are as defined above and

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 C a-C ar-aralkyl-substituted, C až-C ac-acyl, Coy-C ac-acyl, benzoyl optionally substituted in the phenyl by halogen, C 1-C alko alkoxycarbonylmethyl, C 1-Ckarkar alkylcarbonylmethyl up to 4 carbon atoms in the alkyl moiety, equivalent to an inorganic or organic cation or SCCl 3 and SCCl 2 F groups, by treating a compound of formula IV (IV) wherein:

X, R ¹ and R ³ are as defined above, with a compound of formula V

R ² —Z (V) wherein

R ^z is as defined above and

Z is a group that is reactive with an acidic hydrogen atom.

Surprisingly, the five-membered nitrogen-containing heterocyclic compounds produced by the process of the invention exhibit a significantly higher insecticidal activity than prior art carbamates with the same type of activity as 5,6-dimethyl-2-dimethylamino-4-pyrimidinyldimethylcarbamate or 1-naphthyl-4-methylcarbamate ( see U.S. Pat. No. 3,493,574 and U.S. Pat. No. 2,903,478).

In addition, the new five-membered nitrogen-containing heterocyclic compounds exhibit favorable toxicity as well as a systemic effect on plant roots.

Preferably, compounds of formula I are prepared wherein:

R @ ¹ represents a C1 -C6 alkyl group or a phenyl group which is optionally substituted by a C1 -C4 alkyl group, in particular a methyl group and / or one or more identical or different halogen atoms, in particular fluorine or chlorine atoms,

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

R ³ represents CONH 2, CH 2 Cl, CC13, ethoxycarbonylmethyl, fenyloxymethylovou group with one or more halogen atoms in the phenyl part, and

X is SO or

241350

Si (CH3) 2 \

Other preferred compounds of the present invention are those compounds of formula (I) wherein:

R ¹ represents a C 1 -C 4 alkyl group, in particular a methyl group, a tert-butyl group, a phenyl group which is optionally substituted one to three times in the same or different way by halogen, in particular fluorine, chlorine, bromine, iodine, 4 carbon atoms, in particular methyl,

R ² stands for hydrogen, alkyl having 1 to 4 carbon atoms, especially a methyl group, an ethyl group, an alkylcarbonyl group having 1-4 carbon atoms in the alkyl moiety, in particular methylcarbonyl group, an alkenyl group having 3-4 carbon atoms, especially allyl, (C 3 -C 4) alkynyl, in particular propargyl,

R ³ represents CONH 2, CH 2 O, CC13, ethoxycarbonylmethyl, fenyloxymethylovou group with one or more halogen atoms in the phenyl moiety,

R ¹

X is SO or Si (CH 3) 2.

Particular preference is given to compounds of the general formula Ϊ in which:

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

R ² stands for hydrogen, methyl, ethyl, propargyl, trichlormethylsulfenylovou group trlalkylamoniovou group in which the alkyl radicals contain 1 to 4 carbon atoms, morpholinyl,

R ³ represents a group GONH2 and

X is as defined above.

The following compounds of formula I may be mentioned

R ²

ClctCH3

H2C = CH — CH2CH3 CONONa ⁺

CH3

C2H5

Ct

CH,

CH3SO2Na +

CONH2

CONH2

CONH2

CONH2

CONH2

CONH2

CONH2

CONH2

CONH2

Sat Sat Sat Sat Sat Sat Sat (Ο2Η5) 3ΝΗ · ⁾

C0NH2

SO

CH3

CONH2

SO

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

R ¹

R ² R ³ X ci

Cl

Cl

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

Further, the following compounds may 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-Cl 2 -C 6 H 3 OCH 2 - t.butyl n-Gae 3,4-Cl2-C6H3OCH2— t.butyl I-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-Z 2 -CH ₄ - Cl 3.4-C12-C6H3OCH2— t.butyl 4-Cl-CeH4OCH2— t.butyl C 1 -ZO 4 -pH 4 4-C1-C6H4OCH2— t.butyl I-G 3 H 7 4-C1-C6H4QCH2- t.butyl n-C4H9 4-C1-C6H4OCH2— t.butyl C1 -? -? - CR? Cl 4-C1-C6H4OCH2—

R ^z

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-Cl 2 -C 6 H 3

3,4-Cl 2 -C 6 H 3

3,4-Cl 2 -C 6 H 3

3,4-Cl 2 -C 6 H 3

3,4-Cl 2 -C 6 H 3

3,4-Cl 2 -C 6 H 3

3,4-Cl 2 -C 6 H 3

CH3

C2H5

C3H7

1-C 3 H 7 n-C 4 H 9

H 2 C = CH-CH 2 HC = C-CH 2

CH3

C2H5

I1C3H7

I-C3H7

I1-C3H7

HC = C — CH2 — H2C = CH — CH2—

3.4-Cl 2 -C 6 H 3

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-Cl 2 -C 6 H 3

3.4-Cl2-C6H3

3.4-Cl 2 -C 6 H 3

3.4-Cl 2 -C 6 H 3

3.4-C12-C6H3

3.4-Cl 2 -C 6 H 3

3,4-Cl 2 -C 6 H 3

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-C6H13

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

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

L N ll

O

CONH _Z

Compounds of formula IV can be obtained as described in U.S. Pat. No. 241,542 for the preparation of compounds of 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 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 acid chloride, phenyl ester. 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.

Sulfenylating agents such as trihalomethylsulfonic acid chloride, 2,3-trichloromethylsulfenic acid chloride, dichlorofluoromethylsulfenic acid chloride, trifluoromethylsulfenic acid chloride, chloride, optionally substituted phenylsulfenic acid such as phenyl-, β-chlorophenyl-, p-trifluoromethylphenyl-, 3-trifluoromethylphenyl- Of 4-dichlorophenylsulphonic acid.

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, such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, such as ketones such as acetone, methyl ethyl ketone, methylisopropyl ketone and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, and nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, as well as dimethylsulfoxide, tetramethylenesulfone and hexamethylphosphoric triamide.

Suitable acid-binding agents are all customary 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 also aliphatic, aromatic or heterocyclic amines, for example trimethylamine, triethylamine, tributylamine, dimethylaniline, dimethylbenzylamine and pyridine. .

Catalysts which can be used are the compounds which are usually used in the reactions in two-phase systems consisting of water and non-water miscible organic solvents for the phase transfer of the components (phase transfer catalysts). As such, mention may be made in particular of the tetraalkyl and trialkylaralkylammonium salts, preferably of from 1 to 10 carbon atoms, in particular from 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, especially 1 or 2 carbon atoms in the alkyl portion of the aralkyl groups. Particularly suitable are halides, such as chlorides, bromides and iodides, preferably chlorides and bromides. 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 following examples illustrate the process of the invention, but are not intended to 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 is added 40.2 g (0.13 mol) of 5- (3,4-dlchlorophenyl) -5-aminocarbonyl-1,2,3-oxathiadiazolidin-4-one After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure, the residual solid residue was triturated with diethyl ether and dried at room temperature.

43 g (100% of theory) of 5- (3,4-dichlorophenyl) -5-aminocarbonyl-1,2,3-oxathiazolidin-4-one-2-oxide sodium salt are thus obtained which decomposes slowly at a temperature 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 mixture is heated to boiling under stirring for 3 hours, then cooled to 10 ° C and the precipitated crystals are filtered off. diethyl ether and dried at 50 ° C.

120.5 g (70.9% of theory) of 5- (3,4-dichlorophenyl) -5-aminocarbonyl-1,2,3-oxathiazoldin-4-one-2-oxide are thus obtained in the form of slightly yellowish crystals, which melts 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 was added 31.2 g (0.2 mol) of ethyl iodide. The resulting solution was heated at reflux 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, m.p. 112-128 ° C.

The following compounds of formula (Γ) were prepared in an analogous manner to those described in Examples 1 and 2

O = y — jR ² · / / 1 example.

number

R ²

R ³

CH3

SCC12

C0NH2

CONHž

CONHž.

C0NH2 physical properties

melting point 173 to 173.5 ° C viscous oilj viscous oil]

mp 174 ° C

C2H5

CH3

C2H5

CH2-CH-CH2-CH (CH3) 2

CH3

CONH2

CONH2

CON-Hr

CONH2

CONHži

CONH2

CONH2

CONH2 t-C4H9 t-C4H9

mp 135 ° C (decomposition)

mp 174 ° C

1.1; iW ' ^o er

mp 11-11 ° C

1.1.136-138 ° C

m.p. 161-163 ° C, tt.WTBW 168PG '

mp 260 ° C n _D ²⁰ 1.5330

Πύ ²⁰ '1.5280 example number

R ²

R ³ physical physical

CH 2 - C = CH

CH3

-ch _£ o ~ ^CH 2 ° C _Hi O

-CH.0

C.

C2H5 _CH2 — C = CH t-C4H9 t-C4H9 t-C4H9 t-C4H9 n _D ²⁰ 1,5404

mp 110-116 ° C

mp 101-104 ° C

mp 102-104 ° C

terc.C4H9 terc.C4H9

mp 107-108 ° C

mp 91-92 ° C

The compounds of the following examples are also prepared in an analogous manner:

Physical data:

mp 109-114 ° C (from ethanol).

Analysis for:

C20H20Cl3NO4S (molecular weight 476.6)

Example 24% 2Vch ₄ ° - < ^o :

Cl

Example 25 o Cl

CH ₂ N ' _S ' ° or o

Physical data:

mp 126-132 ° C (from ethanol)

Analysis for:

C20H20Cl2N2O6 (MW 487.1) Example 26

Physical data:

m.p. 148-152 ° C (from ethanol)

Analysis for:

C20H20Cl2N2O6 (MW 487.1)

Physical data: resin

Analysis for:

C20H20Cl3NO4S (molecular weight 476.6)

Example 27

Example 31

Whose

IClC-CH / Mxs g

O

Physical data:

mp 123-127 ° C (from ethanol)

Analysis for:

C20H20Cl2N2O6 (MW 487.1)

Example 28

Who, CH _? O

O _? NO> - C H-N ° C

Physical data: mp 94-95 ° C

Analysis for:

C 16 H 18 ClNO 2 S (molecular weight 355.8) Example 32 ° y 2 ' ^CH 2 ⁰ ^ 2X ^Ct

HC = C, CHrNv _S -0

Physical data: resin

Analysis for:

C20H20Cl2N2O6 (MW 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: mp 103-104 ° C

Analysis for:

C16H18CINO4S (molecular weight 355.8)

Physical data:

mp 137-140 ° C (from ethanol)

Analysis for:

C20H19Cl4NO4S (molecular weight 511.3)

Exemplary 34 ct

Whose

O.

y-r

CH £ N s' ° ^Affairs

Whose

Physical data:

mp 109-111 ° C (from ethanol)

Analysis for:

C20H19Cl4NO4S (molecular weight 511.3)

Physical data: high viscosity oil

Analysis for:

C19H23C14NO4S (molecular weight 503.0)

Example 35

O

Analysis for:

C20H19NO4S4 (MW 511.3) Example 39

Physical data:

mp 109-113 ° C (from ethanol)

Analysis for:

C20H20Cl3NO4S (molecular weight 476.6)

Physical data: brittle resin

Example 36

Ct,

Analysis for:

C24H27Cl2NO4S (MW 496.2)

CH 2 N

CK0- <0

Example 40

Physical data: resin ct s

O

O

O

Physical data: brittle resin

Analysis for: C 20 H 20 Cl 3 NO 4 S

Analysis for:

C24H27Cl2NO4S (MW 496.2)

Physical data:

m.p. 97-103 ° C (from ethanol)

Analysis for:

C20H19Cl4NO4S (molecular weight 511.3)

Example 38

Example 41

Physical data:

ct ct

Analysis for:

C24H23Cl2NO4S (MW 492.2)

Example 42

Physical data:

mp 128-132 ° C (from ethanol)

Analysis for: C 24 H 23 Cl 2 NO 4 S

Example 43

CH3N4O

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-CH3N

O

Physical data: viscous oil, n _D ²⁵ 1.5424

Analysis for:

C16H17Cl2NO4S (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 (MW 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 2 O-O / -Cl

Physical data: waxy product

Analysis for:

C16H21Cl2NO4S (Molecular Weight 394.1) Example 51

C 1 -N-sΌ Cl

Physical data: viscous oil, n _D ²⁵ 1.5318

Analysis for:

C17H23Cl2NO4S (MW 408.1) Example 55

Cl

A - »/ Ύ OCa \ XW /

₅ C ij] _M- - o 'cici

Physical data: viscous oil

Analysis for:

C18H25Cl2NO4S (MW 422.1) Example 52

Cl ·

Physical data: viscous oil, n _D ²⁵ 1.5262

Analysis for:

C17H23Cl2NO4S (MW 408.1) Example 56

Cl O .CH ^ - ^^ - Cl _H -CH = CW-CH-N £ a ^'0

Physical data: viscous oil

Analysis for:

C18H25Cl2NO4S (MW 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 2 O ⁰

Physical data: viscous oil, n _D ²⁵ 1.5398

Analysis for:

C17H21Cl2NO4S (molecular weight 406.1 J)

Example 59

Analysis for:

C20H19Cl2NO5S (Molecular Weight 456.1) Example 62

CH 2 -N 4 O 0

Ci cC

Physical data:

viscous oil, n _D ²⁵ 1,5 3 9 2

Analysis for:

C17H20Cl3NO4S (MW 440.6) Example 63

Physical data: viscous oil, n _D ²⁵ 1.5338

Physical data: viscous oil. n _D ²⁵ 1.5282

Analysis for:

C17H21Cl2NO4S (molecular weight 406.1 J)

Analysis for:

C19H24Cl3NO4S (MW 468.6)

Example 60

H? C? C? CH? N? O? C? O

Analysis for:

C16H19Cl2NO4S (MW 392.3J)

Example 61

Physical data:

viscous oil, n _D ²⁵ 1.5519

Analysis for:

C16H18Cl3NO4S (molecular weight 426.5J) Example 65

Physical data:

mp 133-138 ° C (from ethanol)

Physical data:

viscous oil, n _D ²⁵ 1.5442

Analysis for:

C16H18Cl3NO4S (molecular weight 426.5J)

Example 66

Physical data: mp 160-165 ° C

Analysis for:

C20H18Cl2N2O6S (MW 487.1) Example 70

O

Physical data:

mp 107-110 ° C (from ethanol)

Analysis for:

C21H23Cl2NO4S (molecular weight 456.1)

Example 67

Cl

Physical data:

mp 133-134 ° C (from ethanol)

Analysis for:

C20H20CINO5S (molecular weight 421.7)

CiO

Physical data:

viscous oil, n _n ²⁵ 1,5 5 80

Physical data:

mp 119-122 ° C (from ethanol)

Analysis for:

C21H23Cl2NO4S (MW 456.1)

Analysis for:

C20H21CIN2O6S (molecular weight 452.7)

Example 68

CV

Physical data: mp 137-141 ° C

Physical data:

m.p. 148-158 ° C (from ethanol)

Analysis for: C15H17Cl2NO5

Analysis for:

C20H20Cl2N2O6S (MW 487.1)

Example 73

Analysis for:

C16H19Cl2NO4S (molecular weight 392.1)

Analysis for:

C24H24ClNO4S (molecular weight 469.7)

Example 74

^Whose

O

Example 78

O - Cl - Cl

Physical data: resin

Analysis for:

C24H24ClNO4S (MW 492.2)

Physical data: viscous oil, n _D ²⁵ 1.5515

Analysis for:

C18H18ClNO3S (MW 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:

C 16 H 19 Cl 2 NO 6 S (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 2 N x _s .O

Cl o

Physical data:

viscous oil, n _D ²⁵ 1,5421

Analysis for:

C19H26ClNO5S (Molecular Weight 415.7) Example 82

Physical data: viscous oil

Analysis for:

C17H22FNO6S (molecular weight 387.2)

Example 86

O = C

O _{{CH3) 5}

Physical data: viscous oil

Analysis for:

C19H25Cl2NO5S (molecular weight 450.1)

Example 83

Physical data: mp 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: mp 110-115 ° C

Analysis for:

C20H21FN2O6S (molecular weight 436.2)

Example 88

Example 84

o .. A-Oco / OV ··

³ \ _r

Cl

CH, Oy-CH2N-s-OO

Physical data:

melting point 121—123 ° C (from ethanol)

Analysis for:

C21H23Cl2NO4S (molecular weight 456.1)

Physical data:

mp 126-128 ° C

Analysis for:

C21H24FNO4S (molecular weight 405.5)

Example 89

Example 85 o - @ - ^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 , ^{N N} 'S- ° o

Physical data: viscous oil

Analysis for:

C24H22FNO4S (Molecular Weight 441.3) Example 91

Physical data: viscous oil

Analysis for:

C18H26FNO4S (MW 371.5)

CK

^ch a

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 (MW 422.4) Example 96

O

Physical data: viscous oil

Physical data: viscous oil

Analysis for C16H19ClFNO4S

Example 93

Analysis for:

C17H24FNO4S (MW 357.5) Example 97

O

Physical data:

viscous oil

Physical data:

viscous oil

Analysis for:

C17H21Cl2NO4S (molecular weight 406.3)

Example 98

CH _r CH = CW-CW / N 4 -O o

Analysis for:

C17H22FNO4S (molecular weight 355.2)

Example 102

Whose

Physical data: mp 163-166 ° C

Example 99

O

Analysis for:

C20H19CIFNO5S (molecular weight-439.7)

Example 103

CW, = C-CH / N >

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)

ch _l o

O

CH 3 OOC-CH 2 - x ² O ⁰

Physical data: viscous oil

OH

Example 104

C ^ s ^ ^ s- ⁰

O

Analysis for:

C16H20FNO6S (MW 373.2)

Example 101

O

Physical data:

mp 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:

mp 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:

C20H21ClN2O6S (Molecular Weight 452.9) Example 111

r

CH £)

(CH 2 CH-N 4 O

O

^CH Ž ^N ''

Analysis for:

C16H21Cl2NCUS (MW 394.3)

Example 108

Cl

Physical data: viscous oil

Analysis for:

C24H28ClNO4S (Molecular Weight 462.0) Example 112

O

Cí‘ CtPhysical data: mp 125-130 ° C

Analysis for:

C20H19Cl4NO4S (MW 511.3) Example 109

Physical data:

melting point 117-118 ° C (from ethanol)

Analysis for:

C20H20Cl3NO4S (MW 476.8) Example 113

Cl · o

Whose

Physical data:

mp 73-76 ° C (from methanol)

Physical data:

mp 112-111 ° C (from ethanol)

Analysis for:

C20H21CIFNO4S (molecular weight 425.9)

Analysis for:

C20H20Cl3NO4S (molecular weight 476.8)

Example 118

Physical data: mp 128-132 ° C

Cl

ct ct

^{CH 2} (CH 2, q ^CH and ^N

(from ethanol)

Analysis for:

C20H19Cl4NO4S (molecular weight 511.3)

Example 115

ct o

O> F ^CH I ^N 'S ^ ° C for

Physical data: viscous oil

Analysis for:

C18H26CINO4S (molecular weight 387.7)

Example 119

X.η X / CI ^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: C 17 H 24 ClNO 4 S

Example 120

Example 116

CH ^C -CH ^N ^O 0

O

Physical data: mp 81-86 ° C

Analysis for:

C20H21CIFNO4S (molecular weight 425.9)

Physical data: viscous oil

Analysis for: C 17 H 22 ClNO 4 S

Example 121

Example 117

CH 2 CH 2 CH-CH 2 N 4 O

O

Physical data: viscous oil

Analysis for:

C17H22CINO4S

CHjOOC -N.s-CH = ^'0 o

Physical data:

m.p. 58-68 ° C (from ethanol)

Analysis for:

G16H20CINO6S (molecular weight 389.6)

Example 122 Example 126

Physical data: viscous oil

Analysis for:

C17H22ClNO6S (MW 403.9) Example 123

Physical data: mp 171-174 ° C

Analysis for: C 20 H 16 Cl 3 NO 5 S

Example 124

Cl

Physical data: mp 127-128 ° C

Analysis for:

C20H18Cl2FNO5S (molecular weight 474.3)

Example 125

Physical data:

mp 76-78 ° C (from ethanol)

Analysis for:

C20H21Cl2NO4S (molecular weight 442.1)

Physical data:

mp 98-100 ° C (from ethanol)

Analysis for:

C 10 H 20 Cl 3 NO 4 S (molecular weight 476.6) Example 127

CH = CH-CH 2 '5' +

Physical data: viscous oil, no ²⁰ 1.5365

Analysis for:

C16H20CINO4S (MW 357.8) Example 128 ^{0 c} ^ y "> ⁰ - <O

CHfCH-CHfN4O

O

Physical data: viscous oil

Analysis for:

C16H20FNO4S (Molecular Weight 341.4) Example 129

O

Physical data: mp 167-172 ° 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: mp 107-108 ° C

Analysis for:

C20H21Cl2NO4S (molecular weight 378.4)

Example 135

Example 131

Physical data: viscous oil

Physical data: viscous oil

Analysis for: C 16 H 19 Cl 2 NO 4 S

Example 132

O

Physical data:

mp 91-92 ° C

Analysis for:

C20H22ClNO4S (molecular weight 407.8j)

Example 133

Analysis for:

C15H19Cl2NO4S (MW 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:

G16H17Cl2NO1S (molecular weight 390.3)

Example 137

CH 2 O

> CH _from -K _to X) 'Ct ⁰

Physical data:

mp 99-102 ° C (from ethanol)

Analysis for:

C20H20Cl3NO4S (molecular weight 476.6)

Example 138

Example 142

- / oV cp cp

Physical data:

mp 88-90 ° C (from ethanol)

Analysis for:

G20H21Cl2NO4S (MW 442.1) Example 139

O - <-> - »

Physical data: mp 110-116 ° C

Analysis for:

C14H17Cl2NO4S

Physical data: mp 101-104 ° C

Physical data: n _D ^Z0 1.5330

Analysis for: C15H19Cl2NO4S

Analysis for: C 14 H 18 ClNO 4 S

Example 144

Physical data: no ²⁰ 1.5280

Analysis for: C 15 H 20 ClNO 4 S

Example 141

HCzC-CH ^ N ^ S ^'0

Q · ° γΞγ ₄ 0- ^ (O / C?

HCsC-CH -0 £ _NX O

Physical data: mp 101-104 ° C

Analysis for:

C16H17Cl2NO4S

Example 145

Physical data: mp 85-89 ° C

Analysis for: C 18 H 16 ClN 3 CH 2

Physical data: mp 120-121 ° 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.