FR2689129A1 - New 3-mercapto-2-thenoic acid derivs. - and their prepn. from 3-amino-3-thenoate(s) via stable di:thio-carbazate - Google Patents

Abstract

Derivs. of 3-mercapto-2-thenoic acid of formula (I) are new, where m = 1 or 2; R2 = 1-20C alkyl; R4,R5 = H, 1-4C alkyl, phenyl (opt. substd.) or a heterocyclic radical (opt. subst.); or R4+R5 = -CH=CH-CH=CH- or 3-5C alkylene; when m = 1, R3 = H, 1-4C alkyl (opt. substd.), -CS-NHNH2, -CONHR, -CS-NHR, -COOR', -COR'' or -SO2R''; R = aliphatic, cycloaliphatic, arylaliphatic, aromatic or heterocyclic gp., opt. substd.; R' = 1-8C alkyl; R'' = 1-4C alkyl (opt. substd.), phenyl or tolyl; when m = 2, R3 = -CO- or -CO(CH2)nCO-bridge; n = 0-4. USE/ADVANTAGE - (I) are intermediates in herbicide prepn. The claimed prepn. is via stable dithiocarbazates which avoid oxidn. of thiols to disulphides which can occur in prior art.

Description

NOVEL DERIVATIVES OF 3-MERCAPTO-2-THENOIOUE ACID
AND METHODS OF PREPARATION
The present invention relates to the field of thiophene compounds and more particularly to 3-mercapto-2-thenoic acid derivatives.

 Methyl 3- [N- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) ureido-sulfonyl] -2-thenenoate, commonly known as Thiameturon Methyl or Thifensulfuron, is a part of thiophene herbicides claimed in EP 30 142.

These thiophenic compounds are prepared by reacting an aminotriazine or aminopyrimidine with a carbalcoxythiophenesulfonyl isocyanate, itself obtained from a 2-carbalkoxy thiophenesulfonamide, or by reaction of such a sulfonamide with an isocyanato-triazine or -pyrimidine.

The synthesis of 3-mercapto-2-thenoic acid has been described by C. CORRAL et al. in Synthesis 172 (1984) from methyl 3-hydroxy-thenoate and in Organic Preparations and
Procedures 17 (3), 163-167 (1985) from methyl 3-amino-thenoate by diazotization, reaction of diazonium salt with potassium ethylxanthate and hydrolysis of O-ethyl and S- dithiocarbonate ( 2-carbomethoxy-3-thienyl). The second reference (page 164) mentions that the zinc reduction in acidic medium of 2-carbomethoxythiophene-3-sulphochloride does not lead to methyl 3-mercapto-2-thenoate, but to the corresponding disulphide.

 It has now been found that methyl 3-mercapto-2-thenoate and, more generally, alkyl 3-mercapto-2-thenoates can be easily accessed by reacting ethyl and S-dithiocarbonate with hydrazine. - (2-carbalkoxy-3-thienyl). A dithiocarbazate is formed whose acid hydrolysis releases the desired alkyl 3-mercapto-2-thenoate. This thiol can be isolated or not and then reacted with various agents such as, for example, acid halides or anhydrides, isocyanates or isothiocyanates to form 2-carbalkoxy-thiophene derivatives S-substituted in the 3-position.

 The process according to the invention is unexpected since it fails when the hydrazine is replaced by a homologue such as methylhydrazine or by an amine. On the other hand, it has the advantage of providing stable dithiocarbazates which can be used as precursors of alkyl 3-mercapto-2-thenoates and thus make it possible to prevent the oxidation of these thiols to disulfides.

dans laquelle
m est égal à 1 ou 2
R2 représente un radical alkyle en C1 à C20 ;
R4 et R5, identiques ou différents, représentent chacun
un atome d'hydrogène, un radical alkyle en C1 à
C4, un radical phényle éventuellement substitué
ou un radical hétérocyclique éventuellement
substitué, ou forment ensemble un enchainement
-CH=CH-CH=CH- ou alkylène en C3 à C5
si m=l, R3 représente un atome d'hydrogène, un radical
alkyle en C1 à C4 éventuellement substitué ou
un groupement thiocarbazoyle -CS-NHNH2, carba
moyle -CONHR, thiocarbamoyle -CS-NHR, ester
-COOR', acyle -COR" ou sulfonyle -SO2R", où R
représente un reste aliphatique, cycloalipha
tique, arylaliphatique, aromatique ou
hétérocyclique éventuellement substitué, R'
représente un radical alkyle en C1 à C8 et R"
représente un radical alkyle en C1 à C4 éven
tuellement substitué, phényle ou tolyle ;
si m=2, R3 représente un pont -CO- ou -CO(CH2)nCO- où n
est un nombre allant de O à 4.The subject of the invention is therefore thiopheneic compounds of general formula

in which
m is 1 or 2
R2 represents a C1 to C20 alkyl radical;
R4 and R5, identical or different, represent each
a hydrogen atom, an alkyl radical C1 to
C4, an optionally substituted phenyl radical
or a heterocyclic radical
substituted, or together form a concatenation
-CH = CH-CH = CH- or C3 to C5 alkylene
if m = l, R3 represents a hydrogen atom, a radical
optionally substituted C1-C4 alkyl or
a thiocarbazoyl group -CS-NHNH2, carba
average -CONHR, thiocarbamoyl -CS-NHR, ester
-COOR ', acyl -COR "or sulfonyl -SO2R", where R
represents an aliphatic, cycloalipha radical
tick, arylaliphatic, aromatic or
optionally substituted heterocyclic, R '
represents a C1 to C8 alkyl radical and R "
represents a C1 to C4 alkyl radical
substituted, phenyl or tolyl;
if m = 2, R3 represents a bridge -CO- or -CO (CH2) nCO- where n
is a number from 0 to 4.

 The alkyl radical R 2 can be linear or branched, and preferably contains 1 to 12 carbon atoms. A radical R2 which is more particularly preferred is the methyl radical.

 As examples of substituents of the phenyl radical which may represent R4 and / or R5, there may be mentioned more particularly halogen atoms and C1-C4 alkyl or alkoxy radicals.

 As examples of heterocyclic radicals that may represent R4 and / or R5, there may be mentioned 2- or 3-thienyl, 2-benzo [b] thienyl or 2-benzo [b] furyl radicals optionally substituted by a halogen atom or a radical. alkyl.

 When R4 and R5 together form an alkylene chain, it may be for example a trimethylene radical, tetramethylene, 1 or 2-methylbutylene.

 As examples of residues R, C 1 -C 8 alkyl, cyclohexyl, benzyl, p-phenethyl, phenyl, triazinyl or pyrimidinyl may be mentioned more particularly, these radicals possibly being substituted by halogen atoms or alkyl or alkoxy groups. or nitro.

 As possible substituents of the alkyl radical which R "may represent, there may be mentioned more particularly the halogen atoms and the amino (for example butylamino) or ester groups such as -COOR '.

qui constituent l'accès aux autres dérivés de formule (I), sont préparés par diazotation des 3-amino-2-thénoates d'alkyle correspondants de formule

puis réaction du sel de diazonium avec un alkylxanthate alcalin MS-CS-OQ (M=Na ou K et Q=méthyl, éthyl ou propyl) et enfin réaction avec l'hydrazine du dithiocarbonate d'O-alkyle et de S-(2-carbalcoxy-3-thiényle).The compounds according to the invention in which m = 1 and R 3 is a thiocarbazoyl radical, that is to say the dithiocarbazates of general formula

which constitute the access to the other derivatives of formula (I) are prepared by diazotisation of the corresponding alkyl 3-amino-2-thenoates of formula

then reaction of the diazonium salt with an alkali metal alkylxanthate MS-CS-OQ (M = Na or K and Q = methyl, ethyl or propyl) and finally reaction with the hydrazine of O-alkyl dithiocarbonate and S- (2 -carbalcoxy-3-thienyl).

The first two steps (diazotation and reaction with
MS-CS-OQ) can be carried out under the same operating conditions as those described in the aforementioned reference
Organic Preparations and Procedures. The third step which is the originality of the present invention can be carried out at a temperature ranging from -10 to +400C, preferably at room temperature, in an inert solvent such as, for example, ethanol, methanol, propanol, ether, dioxane, tetrahydrofuran, acetonitrile or dimethylformamide. A polar solvent is preferably used. The hydrazine / dithiocarbonate molar ratio can range from 1 to 3, but is preferably from 1.3 to 2.

 The hydrazine is preferably employed in the form of hydrazine hydrate, but it would not depart from the scope of the present invention using anhydrous hydrazine.

obtenu conformément à la méthode décrite par J.Liebscher et al. dans Journal f.prakt. Chemie, 325(6), 915-8(1983) à partir de la cétone correspondante R5-COCH2-R4. Some of the alkyl 3-amino-2-thenoates of formula (II), used as starting materials, are already described in the literature: see, for example, DE 1,055,007 and the articles of PRHuddleston et al in Synth. Common. 9, 731 (1979), K.Schollberg et al. in J.Pr.Chem. 325 (5), 87679 (1983) and H.Hartmann et al. in Synth. Common. 2756 (1984). In general, the compounds of formula (II) can be prepared by reaction of an alkyl thioglycolate
HS-CH2COOR2 (III) with a suitably arranged nitrile in the presence of a base. Thus, to prepare unsubstituted 3-amino-2-thenoates (II) at positions 4 and 5 (R4 = R5-H), the method of PR Huddleston et al. reacting thioglycolate (III) with 2-chloroacrylonitrile. The 3-amino-2-thenoates (II) substituted in the 5-position or in the 4 and 5-positions can be prepared according to the method described by H.Hartmann et al. by reacting thioglycolate (III) with a 3-chloro-acrylonitrile of formula

obtained according to the method described by J.Liebscher et al. in Journal f.prakt. Chemie, 325 (6), 915-8 (1983) from the corresponding ketone R5-COCH2-R4.

où Y désigne un radical méthyle, phényle ou tolyle. Cette réaction est avantageusement effectuée à température ambiante par addition lente du nitrile (IV-b) à un mélange de thioglycolate (III) et de méthylate de sodium. Le nitrile (IV- b) peut être obtenu de façon connue en soi par action du méthylate de sodium sur l'acétonitrile R4-CH2CN correspondant et réaction du dérivé R4-C(CN) = CHONa ainsi formé avec un sulfochlorure Y-SO2Cl.The 4-substituted 3-amino-2-thenoates (II) can be prepared by reacting the thioglycolate (III) with a nitrile of the formula

where Y denotes a methyl, phenyl or tolyl radical. This reaction is advantageously carried out at room temperature by slow addition of the nitrile (IV-b) to a mixture of thioglycolate (III) and sodium methoxide. The nitrile (IV-b) can be obtained in a manner known per se by the action of sodium methoxide on the corresponding acetonitrile R4-CH2CN and reaction of the derivative R4-C (CN) = CHONa thus formed with a sulfochloride Y-SO2Cl.

qui peut être isolé ou non avant d'être mis en contact avec divers réactifs pour former les autres composés de formule (I) selon l'invention.Treatment of a dithiocarbazate (Ia) with an acidic medium releases the corresponding thiol of formula

which can be isolated or not before being brought into contact with various reagents to form the other compounds of formula (I) according to the invention.

 The acidic treatment of the dithiocarbazate (Ia) is advantageously carried out at room temperature by means of a quantity of aqueous solution of hydrochloric acid at 10% sufficient to obtain the complete dissolution of the dithiocarbazate and a quantity of a solvent (ethyl ether or ethyl acetate) sufficient to extract the liberated thiol (Ib).

As reagents capable of reacting with the thiol (I-b), mention may be made more particularly
(1) aliphatic, cycloaliphatic, arylaliphatic, aromatic or heterocytic isocyanates and isothiocyanates such as, for example, isocyanates and isothiocyanates of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cyclohexyl, benzyl, phenethyl, α-methylbenzyl, phenyl; , tolyl, methoxyphenyl, chloro- or fluorophenyl, dichlorophenyl, nitrophenyl or 4-methoxy-6-methyl-1,3,5-triazinyl, resulting in compounds (I) wherein R3 is a carbamoyl or thiocarbamoyl group;
(2) alkyl chloroformates such as, for example, methyl, ethyl, butyl, hexyl or octyl chloroformates leading to compounds (I) in which R3 is an ester group
(3) anhydrides and acid halides such as, for example, acetic anhydride, butyric anhydride and chloroacetyl chlorides, 5-chlorovaleryl, 3-carbomethoxypropionyl, ethylmalonyl, 5-carbomethoxypentanoyl, 3-octyloxycarbonylpropionyl benzoyl or tosyl, resulting in the compounds (I) in which R 3 is an acyl or sulfonyl group;
(4) optionally substituted haloalkanes such as, for example, methyl iodide, 2-chloroethanol, benzyl, methylbenzyl, 2,3- (or 3,4) dichlorobenzyl chlorides or (2-chloroethanol) chlorides; - or 3-thienyl) methyl, and ethyl bromides, cyclopentylmethyl or cyclohexylmethyl, leading to the compounds (I) in which
R3 is an optionally substituted alkyl radical
(5) phosgene and dichlorides of diacids such as, for example, oxalyl, malonyl, succinyl, glutaryl or adipoyl dichlorides, which lead to the compounds (I) in which m = 2.

 These reactions are advantageously carried out under reflux in an inert solvent such as, for example, dichloromethane, dioxane, benzene, toluene or xylene, using stoichiometric amounts of thiol (Ib) and reagent (1) to ( 5).

 The following examples illustrate the invention without limiting it.

EXAMPLE 1
12.5 g (0.079 moles) of methyl 3-amino-2-thenenoate were stirred at room temperature, to which 100 ml of 40% hydrochloric acid was added. The resulting solution is stirred for one hour at room temperature and then cooled to OOC with an ice bath. A solution of 5.5 g (0.079 mol) of sodium nitrite in 20 ml of water is then added dropwise, and then a solution of 11 g (0.095 mol) of carbonate is added very slowly over one hour. of sodium and 12.75 g (0.079 mol) of potassium ethylxanthate in 100 ml of water. The mixture is then heated to 600C until the end of the nitrogen evolution (about one hour).

 After cooling, the mixture is extracted with 700 ml of ether and washed with a 10% sodium hydroxide solution and then with 500 ml of water. The ether phase is then decanted, dried over magnesium sulfate, decolorized on animal charcoal, then filtered and concentrated under reduced pressure. 16 g of O-ethyl dithiocarbonate and S- (2-carbomethoxy-3-thienyl) are obtained in the form of a thick red oil, which is reacted at room temperature with 4.6 g of hydrazine hydrate. solution in 120 ml of ethanol. The precipitate obtained is then filtered off and washed with 50 ml of acetonitrile and then with 100 ml of ether. 8.4 g of 2-carbomethoxy-3-thienyl dithiocarbazate are thus obtained in the form of a white powder which melts at 1100 C and whose elemental analysis for C7H8N2O2S3 confirms the announced structure.

 IR spectrum (KBr): 3160, 1580 (NHNH 2); 1680 (CO); 1460, 1420, 1375, 1225, 940, 875 and 745 cl.

NMR spectrum (DMSO d6): NH4: 6.67; 6H5: 7.03; 6H,
NHNH 2: 6.63; 6H, CH3: 3.63.

EXAMPLE 2
The procedure is as in Example 1 but replacing the methyl 3-amino-2-ethenoate with methyl 3-amino-4-methyl-2-thenenoate. For 12 g (0.07 mole) of this compound, 4.83 g of sodium nitrite, 8.95 g of sodium carbonate, 11.23 g of potassium ethylxanthate and 4.4 g of hydrazine hydrate.

 9 g of 2-carbomethoxy-4-methyl-3-thienyl dithiocarbazate are thus obtained in the form of a light yellow powder which melts at 120 ° C. and whose elemental analysis for C 8 H 10 N 2 O 2 S 3 confirms the expected structure.

IR spectrum (KBr): 3320, 1605 (NHNH 2); 1670 (CO); 1440, 1395, 1235, 955 and 785 cm.
1H NMR Spectrum (DMSO d6)
# H, H5: 7.06; 6H, CH3: 3.67 and 2.07; 6H, NHNH 2: 6.77.

EXAMPLE 3
The procedure is as in Example 1 but replacing the methyl 3-amino-2-ethenoate with methyl 3-amino-4,5-dimethyl-2-thenenoate. For 20 g (0.108 mole) of this compound, 7.45 g of sodium nitrite, 12.29 g of sodium carbonate, 17.82 g of potassium ethylxanthate and 6.2 g of sodium hydrate are used. hydrazine.

13 g of 2-carbomethoxy-4,5-dimethyl-3-thienyl dithiocarbazate are thus obtained in the form of a light yellow powder which melts at 13 ° C. and whose elemental analysis for
CgH12N202S3 confirms the expected structure.

IR spectrum fKBr): major bands at 3420, 3220 (NHNH2); 1660 (CO); 1440, 1245, 1080, 835 and 770 cm 1
NMR spectrum (DMSO d6): 6H, NHNH 2: 5.66; 6H, CH3 3.53, 2.16 and 1.93
EXAMPLE 4
With stirring and at room temperature, 10 g (0.048 mol) of 3-amino-2-carbomethoxy-benzothiophene are dissolved in 100 ml of 50% hydrochloric acid. Stirring is maintained for 30 minutes at room temperature, and then the solution is cooled with OOC using an ice bath. A solution of 3.33 g (0.048 mol) of sodium nitrite in 15 ml of water is then added dropwise, the temperature being maintained around OOC throughout the addition.

 The solution is stirred for another hour at OOC and allowed to come to room temperature. To the stirred solution is then added very slowly a solution of 6.16 g (0.058 mole) of Na2CO3 and 7.70 g (0.052 mole) of potassium ethylxanthate in 125 ml of water. The precipitate formed during the addition is stirred and gradually heated to 60 ° C. in a water bath, and the heating and stirring are maintained until the end of the nitrogen evolution, ie about one hour.

After cooling, the solution obtained is extracted with ethyl ether, washed with a 10% sodium hydroxide solution and then with water, decanted, dried over magnesium sulphate, decolorized with animal charcoal, filtered and then evaporated. under reduced pressure. 10.8 g of a red-colored oil consisting of ethyl dithiocarbonate and S- (2-carbomethoxy-3-benzo [b] thienyl) are thus obtained.
IR spectrum (KBr): Main bands at 3450, 2990, 2960, 1725, 1500, 1445, 1370, 1240, 1095, 1035, 820, 755 and 730 cm1.

 With stirring and at room temperature, 10 g (0.032 mol) of this oil are dissolved in 60 ml of ethanol, and then 2.4 g of hydrazine hydrate are added dropwise. A pale yellow precipitate is rapidly formed, which is stirred for 30 minutes, then filtered off and washed successively with ethanol and acetonitrile.

 There is thus obtained 4 g of 2-carbomethoxy-3-benzo [b) thienyl dithiocarbazate which melts at 1540C and whose centesimal analysis confirms the empirical formula C1 1 HloN 2 O 2 S 3.

IR spectrum (KBr): main bands at 3300, 2960, 2900, 1695, 1470, 1250, 1230, 1100, 1060, 950, 930, 820, 760 and 740 cm1
NMR Spectrum (DMSO d6): 6H4, H7: 8.10; 6H5, H6 7.40; NH, CH3: 3.70; 6NHNH 2: 7.20.

EXAMPLE 5
12 g (0.0385 mol) of dodecyl 3-amino-2-ethenoate were stirred at room temperature, to which 100 ml of 50% hydrochloric acid was added. The resulting solution is stirred for 45 minutes, then cooled to OOC using an ice bath. A solution of 2.92 g (0.0423 mol) of sodium nitrite in 15 ml of water is then added dropwise, followed by stirring for one hour.

 To the solution cooled to room temperature, a solution of 4.40 g (0.0423 mol) of sodium carbonate and 6.16 g (0.0385 mol) of potassium ethyxanthate in 100 ml is added very slowly. of water. The mixture is gradually heated to 600 ° C. and then at 80 ° C. for 35 minutes.

 After cooling, the solution obtained is extracted with ethyl ether, washed with a 10% sodium hydroxide solution and then with water, decanted and dried, and then concentrated under reduced pressure.

 9 g of methyl dithiocarbonate and S- (2-carbododecyloxy-3-thienyl) are obtained in the form of a red oil which is dissolved in 70 ml of anhydrous ether before adding 2.16 g of hydrate. hydrazine with stirring. The precipitate formed in 5 minutes is then filtered off and then washed successively with 50 ml of acetonitrile and with 50 ml of anhydrous ether.

 There is thus obtained 3 g of 2-carbododecyloxy-3-thienyl dithiocarbazate in the form of a light brown powder which melts at 970C and whose percentage analysis is in accordance with the empirical formula C18H30N20253.

IR spectrum (KBr); 3340 and 3230 (NHNH2); 1680 (CO)
NMR Spectrum (DMSO d6): EH H5: 7.06; H4: 6.51; 6H, NHNH 2: 5.46; NH, CH 2: 3.96 and 1.23; 6H, CH3: 0.8.

ont été préparés en opérant comme à l'exemple 1 à partir des 3-amino-2-thénoates de méthyle R4 et/ou R5 substitués correspondants. Leurs caractéristiques sont rassemblées dans le tableau suivant.

EXAMPLES 6 to 15
Other dithiocarbazates of formula

were prepared by operating as in Example 1 from the corresponding substituted R4 and / or R5 methyl 3-amino-2-thenoates. Their characteristics are summarized in the following table.

<SEP><SEP><SEP><SEP> IR (KBr) <SEP><SEP> Spectrum of <SEP> NMR Spectrum
<tb> EXAMPLE <SEP> R4 <SEP> R5 <SEP> Merge <SEP> v <SEP> cm- <SEP> DMSO <SEP> d6
<tb><SEP> (C)
<tb><SEP> 6 <SEP> hydrogen <SEP> phenyl <SEP> 124 <SEP> 3340, <SEP> 3220, <SEP> 1610 <SEP> (NHNH2) <SEP>#H,<SEP> H4: 7.50; # H, C6H5: 7.50 <SEP> and <SEP> 7.30 <SEP>;
<tb><SEP> 1680 <SEP> (CO) <SEP>#H (NHNH2): 5.73 <SEP>;<SEP>#H,<SEP> CH3: 3.63
<tb><SEP> 7 <SEP> phenyl <SEP> hydrogen <SEP> 122 <SEP> 3340, <SEP> 3220 <SEP> (NHNH2) <SEP># H, H5: 7.66 <SEP>;<SEP># H, C6H5: 7.15 <SEP>;
<tb><SEP> 1675 <SEP> (CO) <SEP>#H (NHNH2): 5.73 <SEP>;<SEP># H, CH3: 3.63
<tb><SEP> 8 <SEP> p-chloro <SEP> hydrogen <SEP> 130 <SEP> 3340, <SEP> 3220, <SEP> 2900, <SEP> 2580 <SEP># H, H5: 7 , 36; # H, C6H4: 7.70 <SEP> and <SEP> 7.23 <SEP>;
<tb><SEP> phenyl <SEP> (NHNH2), <SEQ> 1675 <SEP> (CO) <SEP>#H (NHNH2): 6.13 <SEP>;<SEP># H, CH3: 3, 60
<tb><SEP> 9 <SEP> p-Fluoro- <SEP> Hydrogen <SEP> 120 <SEP> 3350, <SEP> 2900, <SEP> 2560 <SEP> (NHNH2) <SEP># H, H5: , 36; #, C6H4: 7.66 <SEP> and <SEP> 7.00 <SEP>;
<tb><SEP> phenyl <SEP> 1680 <SEP> (CO) <SEP>#H (NHNH2): 6.66 <SEP>;<SEP>#H,<SEP> CH3: 3.63
<tb><SEP> 10 <SEP> p-bromo <SEP> hydrogen <SEP> 126 <SEP> 3350, <SEP> 2900, <SEP> 2580 <SEP> (NHNH2) <SEP>#H,<SEP> HS: 7.43, #H, <SEP> C6H4: 7.63 <SEP> and <SEP> 7.36 <SEP>;
<tb><SEP> phenyl <SEP> 1680 <SEP> (CO) <SEP>#H (NHNH2): 6.33 <SEP>;<SEP># H, CH3: 3.66
<tb><SEP> 11 <SEP> Hydrogen <SEP> p-Fluoro- <SEP> 136 <SEQ> 3340, <SEP> 3240 <SEP> (NHNH2) <SEP># H, H4: 7,15; # H, <SEP> C6H4: 7.61 <SEP> and <SEP> 7.26 <SEP>;
<tb><SEP> phenyl <SEP> 1675 <SEP> (CO) <SEP>#H (NHNH2): 6.26 <SEP>;<SEP># H, CH3: 3.73
<tb><SEP> 12 <SEP> Hydrogen <SEP> p-tolyl <SEP> 162 <SEQ> 3340, <SEP> 3220 <SEP> (NHNH2) <SEP>#H,<SEP> H4: 7.18 ## STR5 ## and SEP> 7.08 <SEP>;
<tb><SEP> 1690 <SEP> (CO) <SEP>#H (NHNH2): 5.40 <SEP>;<SEP># H, CH3: 3.66 <SEP> and
<tb><SEP> 2.28
<tb><SEP> 13 <SEP> hydrogen <SEP> 2-benzo- <SEP> 126 <SEP> 3320, <SEP> 3250 <SEP> (NHNH2) <SEP># H, H4: 7.40 <SEP >;#H,<SEP> benzofuran: <SEP> 7.85
<tb><SEP> [b] furyl <SEP> 1700 <SEP> (CO) <SEP> 7.63 <SEP> and <SEP> 7.30
<tb><SEP>#H (NHNH2): 6.56 <SEP>;<SEP># H.CH3: 3.56
<tb><SEP> 14 <SEP> -CH2CH2CH2- <SEP> 135 <SEP> 3340, <SEP> 3240 <SEP> (NHNH2) <SEP>#H (NHNH2): 5.95 <SEP>;<SEP># H, CH3: 3.60
<tb><SEP> 1670 <SEP> (CO) <SEP>#H,<SEP> (CH2) 3: 2.73 <SEP> and <SEP> 2.40
<tb><SEP> 15 <SEP> -CH2CH2CH2CH2- <SEP> 74 <SEP> 3260, <SEP> 32120 <SEP> (NHNH2) <SEP>#H (NHNH2): 5.23 <SEP>;<SEP># H, CH3: 3.63
<tb><SEP> 1665 <SEP> (CO) <SEP>#H,<SEP> (CH2) 4: 2.60, <SEP> 2.40 <SEP> and <SEP> 1.73
<Tb>
The dodecyl 3-amino-2-thenoate, used for the preparation of the dithiocarbazate of Example 5, was synthesized from 2-chloro-acrylonitrile as follows:
72.8 g (0.28 mole) of dodecyl thioglycolate are added dropwise to a solution of 600 ml of anhydrous ether containing 27.3 g (0.7 mole) of sodium amide while maintaining the temperature at room temperature. about 250C. After the addition is complete, stirring is continued for 30 minutes and the mixture is then cooled to OOC. At this temperature, a solution of 24.5 g (0.28 mol) of 2-chloroacrylonitrile in 35 ml of anhydrous ether was added dropwise, and the mixture was stirred for one and a half hours at room temperature.

After allowing the excess sodium amide to settle, the ethereal solution is slowly poured into 500 ml of water. The ether phase is stirred, then decanted, dried, decolorized and filtered. After passing a stream of gaseous hydrochloric acid, the precipitate formed is filtered off, dried and recrystallized from ethanol. There is thus obtained the hydrochloride of dodecyl 3-amino-2thenoate which, after treatment with a solution of sodium hydrogen carbonate, gives 22.4 g of dodecyl 3-amino-2-thenoate which melts at 570C.

IR (KBr): 3460, 3350 (NH2); 1660 (CO) cm 1
1H NMR Spectrum (DMSO d6)
6H4: 6.53; H, 7.43; 6HN2: 6.36; ECH2: 4.06, 1.56 and 1.20; SCH3: 0.80.

By operating in the same way from the 2-ethylhexyl thioglycolate, 2-ethylhexyl 3-amino-2-thenoate is obtained in the form of an oil having the following characteristics:
IR tKBr spectrum: 3480, 3380 (NH 2); 1670 (CO) cm 1
1H NMR Spectrum (DMSO d6)
6H4: 6.43; 6H5: 7.33; 6NH2: 6.26; 6CH2: 3.93 and 1.20; 6CH3: 0.80.

Methyl 3-amino-4-phenyl-2-thenoate, used for the preparation of the dithiocarbazate of Example 7, was synthesized from phenylacetonitrile proceeding as follows:
50 g of phenylacetonitrile are slowly added to a solution of sodium methoxide obtained from 11.78 g of sodium and 750 ml of methanol and the temperature is maintained at 400 ° C. by means of an ice bath. The precipitate formed in one hour is then drained and dried in the open air.

 The sodium derivative C6H5C (CN) = CHONa thus obtained (49 g) is stirred in 200 ml of dimethylformamide at room temperature, and then 51.71 g of benzenesulphonyl chloride are slowly added in small portions. After stirring for 3 hours, the solution is poured into 2.5 l of cold water with stirring.

The precipitate formed is then drained, washed with water and dried in the open air.

 The sulfonyl derivative C6H5C (CN) = CH-OSO2C6H5 thus obtained (60 g) is added in small portions over one hour to a mixture of 22.26 g of methyl thioglycolate in a solution of sodium methoxide obtained from 10, 14 g of sodium and 300 ml of methanol. After stirring for 3 hours at room temperature, the solution is poured into water with stirring and the precipitate formed is drained and dried, and then recrystallized from ethyl acetate. 46 g of methyl 3-amino-4-phenyl-2-thenenoate are thus obtained in the form of a whitish powder which melts at 700 ° C.

utilisés pour la synthèse des dithiocarbazates des exemples 8 à 10.Leurs caractéristiques sont rassemblées dans le tableau suivant

IR spectrum (KBr): 3450, 3360 (NH2); 1650 (CO); 1440,1300,1085,775 and 700 cm-
1H NMR Spectrum (DMSO d6):
6H5: 7.56; SH, NH 2: 6.20; 6H, C6H5: 7.36; EH, CH3 3.75
Working in the same way from the corresponding p-halophenylacetonitrile, the methyl 3-amino-4- (p-halophenyl) -2-thenoates of formula

used for the synthesis of the dithiocarbazates of Examples 8 to 10.Their characteristics are summarized in the following table

<tb><SEP><SEP> Point of
<tb><SEP> merger <SEP><SEP> IR (KBr) spectrum <SEP><SEP> Spectrum of <SEP> 1H NMR
<tb><SEP> X <SEP> (solvent
<tb><SEP> of <SEP> recrysts <SEP> v <SEP> cm- <SEP> (DMSO <SEP> d6)
<tb><SEP> tallization)
<tb> chlorine <SEP> 1010C <SEP> 3450, <SEP> 3340 <SEP>(NH2);<SEP> 6H5: 7.60 <SEP>;<SEP> 6C6H4: 7.43 <SEP>
<tb><SEP> (ether) <SEP> 1665 <SEP> (CO) <SEP> 6NH2: 6.26 <SEP>;<SEP> 6CH3: 3.73 <SEP>
<tb> fluorine <SEP> 124 C <SEP> 3480, <SEP> 3370 <SEP>(NH2);<SEP> 6H5: 7.56 <SEP>;<SEP> 6C6H4: 7.40 <SEP>
<tb><SEP> (mixture <SEP> 2/3 <SEP> 1660 <SEP> (CO) <SEP> and <SEP> 7.23 <SEP>;<SEP> 6NH2: 6.20 <SEP>;
<tb><SEP> Ether / acetate <SEP># CH3: 3.75
<tb><SEP> of <SEP> ethyl) <SEP>
<tb> bromine <SEP> 118 C <SEP> 3450, <SEP> 3340 <SEP> (NH2) <SEP>;<SEP># H5: 7.58 <SEP>;<SEP># C6H4: 7.53
<SEQUENCEID>(SEQ)>SEP> 1665 <SEP> (CO) <SEP> and <SEP> 7.30 <SEP>;<SEP># NH2: 6.15 <SEP><SEP>;
<tb><SEP> 6CH3: 3.65 <SEP>
<Tb>
Methyl 3-amino-5- (2-benzo [b] furyl-2-thenenoate, used for the synthesis of the dithiocarbazate of Example 13, was prepared from 2-acetylbenzo [b] furan by proceeding as follows
69.14 g of phosphorus oxychloride are added dropwise to 91.1 g of dimethylformamide and then the mixture is stirred until the temperature is approximately 200 ° C. 50 g of 2-acetylbenzo [b] furan are then slowly added. After the addition was complete, the solution was heated at 60 ° C. for 30 minutes and then 43.36 g of hydroxylamine hydrochloride were added in small portions at a temperature below 900 ° C. After stirring for 30 minutes, 250 ml of hot water are added, and then the aqueous solution is extracted with ethyl ether. After treatment of the ethereal phase, 96 g of 3- (2-benzo [b] furyl) -3-chloro-acrylonitrile as an oil which is dissolved in 90 ml of methanol.

 The solution thus obtained is then added dropwise at a temperature below 400C to a solution, freshly prepared, of 50 g of methyl thioglycolate and 22.7 g of sodium in 300 ml of methanol. After stirring for one hour at ambient temperature, the mixture is poured into 2 liters of water and the precipitate formed is drained, washed with water and dried, and then recrystallized from a 3/2 mixture of ethyl ether and ethyl acetate. ethyl acetate.

 There is thus obtained 42 g of methyl 3-amino-5- (2-benzo [b] furyl) -2-thenenoate in the form of an orange powder which melts at 157 ° C.

IR spectrum (KBr) v cm 1:
3470, 3360, 1595 (NH 2), 1665 (CO)
1H NMR Spectrum (DMSO d6)
EH, benzofuran: 7.53, 7.21 and 7.00; 6H4 (thiophene) 7.21; 6H, NH 2: 6.55; NH, CH3: 3.68
The 3-amino-2-thenoates, used for the synthesis of the dithiocarbazates of Examples 14 and 15, were prepared in the same way, but replacing 2-acetylbenzo [b] furan by cyclopentanone and cyclohexanone respectively.

Methyl 3-Amino-4,5-trimethylene-2-thenoate
Melting point: 1240C
IR spectrum (KBr) v cm 1: 3480, 3350 (NH 2), 1665 (CO)
NMR spectrum (DMSO-d6): # NH2: 6.36; 6CH3: 3.60; SCH2: 2.68 and 2.40
Methyl 3-Amino-4,5-tetramethyl-2-thenenoate (hydrochloride)
Melting point: 1180C
IR spectrum (KBr) v cm 1: 2500, 2710 (NH 3 + Cl), 1710 (CO)
NMR spectrum (DMSO-d6): # NH3 + Cl-: 8.50; # CH3: 3.60; SCH2: 2.53, 2.26 and 1.63
The following table summarizes other 3-amino-2-thenoates of formula (II) prepared according to one or the other of the preceding methods.

<Tb>

<SEP> R2 <SEP> R4 <SEP> R5 <SEP><SEP> Point of
<tb><SEP> merge <SEP> (C)
<tb><SEP> methyl <SEP> p-tolyl <SEP> hydrogen <SEP> 79
<tb><SEP> p-methoxyphenyl <SEP> n <SEP><SEP> 105
<tb><SEP> 2-thienyl <SEP>"<SEP><SEP> 91
<tb><SEP>"<SEP> 3-thienyl <SEP>"<SEP> 95
<tb><SEP> hydrogen <SEP> 5-chloro-2-thienyl <SEP> 71
<tb><SEP>"<SEP>"<SEP> 2-benzo [b] thienyl <SEP> 110
<tb><SEP>"<SEP>"<SEP> 3-methyl-2-benzod [b] <SEP> 133
<tb><SEP> thienyl
<tb><SEP> methyl <SEP> phenyl <SEP> 114
<tb> -CH (CH3) -CH2CH2CH2- <SEP> 124a
<tb> -CH2-CH (CH3) <SEP> -CH2CH2- <SEP> 100a
<tb><SEP> n-octyl <SEP> hydrogen <SEP> hydrogen <SEP> 106a
<tb><SEP> methyl <SEP>"<SEP><SEP> 74a
<tb><SEP> hydrogen <SEP> phenyl <SEP> 74
<tb><SEP>"<SEP>"<SEP> 4-fluorophenyl <SEP> 126a
<tb><SEP>"<SEP> -CH2CH2CH2CH2- <SEP> 90a
<tb><SEP> 2-ethyl
<tb><SEP> hexyl <SEP> -CH = CH-CH = CH- <SEP> (oil)
<tb> n-dodecyl <SEP> hydrogen <SEP> 2-benzo [b] furyl <SEP> 122
<tb> a = hydrochloride
EXAMPLE 16
1.5 g (0.006 mol) of the 2-carbomethoxy-3-thienyl dithiocarbazate of Example 1 are stirred for 10 minutes at room temperature in 70 ml of a 10% aqueous solution of hydrochloric acid and 100 ml of ethyl ether. The mixture is decanted and the ether phase is washed with 150 ml of water, dried over magnesium sulphate and then evaporated under reduced pressure at 400 ° C.

 0.94 g of methyl 3-mercapto-2-thenoate is thus obtained in the form of a yellow oil whose elemental analysis corresponds to the empirical formula C 6 H 60 O 2 S 2.

 IR spectrum (KBr) v cm 1: 2500 (SH); 1680 (CO).

 NMR Spectrum (DMSO-d6):? H, H4: 7.15; 6H, H5: 7.60; NH, CH3: 3.80; EH, SH: 6.10.

dont les caractéristiques sont rassemblées dans le tableau suivant

EXAMPLES 17 TO 21
By operating as in Example 16 from the dithiocarbazates of Examples 2, 8 to 10 and 4, 3-mercapto-2-thenoates of formula

whose characteristics are summarized in the following table

<tb> EX <SEP><SEP><SEP><SEP> IR <SEP> Spectrum <SEP> Spectrum of <SEP> NMR
<tb><SEP> R4 <SEP> R5 <SEP> merge
<tb><SEP> (C) <SEP> (KBr) <SEP><SEP> cm- <SEP> (DMSO <SEP> d6)
<tb><SEP> 17 <SEP> CH3 <SEP> H <SEP> - <SEP> 2500 <SEP> (SH) <SEP># H5 <SEP><SEP>:<SEP> 7.60
<tb><SEP> (oil) <SEP> 1675 <SEP> (@@) <SEP><SEP>## H <SEP><SEP>:<SEP> 6 <SEP> 20
<tb><SEP># CH3 <SEP><SEP>:<SEP> 3.90 <SEP> and
<tb><SEP> 2.20
<tb><SEP> 2500 <SEP> (SH) <SEP> 6H5 <SEP>: <SEP> 7.83
<tb><SEP> 18 <SEP> p -ClC6H4 <SEP> H <SEP> 121 <SEP> 1680 <SEP> (CO) <SEP> 6C6H4 <SEP>: <SEP> 7.40
<tb><SEP>#SH<SEP><SEP>:<SEP> 6.26
<tb><SEP># CH3 <SEP><SEP>:<SEP> 3.76
<tb><SEP> 2500 <SEP> (SH) <SEP> 6H5 <SEP>: <SEP> 7.86
<tb><SEP> 19 <SEP> @ <SEP><SEP> H <SEP> 116 <SEP> 1670 <SEP> (CO) <SEP>& 6H4 <SEP>: <SEP> 7,43 <SEP> and
<tb><SEP> p-FC6H4 <SEP> 7.23
<tb><SEP>#SH<SEP><SEP>:<SEP> 6.30
<tb><SEP> 6CH3 <SEP>: <SEP> 3.48
<tb><SEP> 2500 <SEP> (SH) <SEP># H5 <SEP><SEP>:<SEP> 7.86
<tb><SEP> 20 <SEP> H <SEP> 114 <SEP> 1680 <SEP> (CO) <SEP># C6H4 <SEP><SEP>:<SEP> 7.53 <SEP> and
<tb><SEP> p-BrC6H4 <SEP> 7.23
<tb><SEP> 6SH <SEP>: <SEP> 6.26
<tb><SEP> 6CH3 <SEP>: <SEP> 3.73
<tb><SEP> 2540 <SEP> (SH) <SEP> NH4, H7 <SEP>: <SEP> 8.00
<tb><SEP> 21 <SEP> -CH = CH-CH = CH- <SEP> 76 <SEP> 1690 <SEP> (CO) <SEP> 6H5, H6 <SEP>: <SEP> 7.55
<tb><SEP>#SH<SEP><SEP>:<SEP> 6,40
<tb><SEP># CH3 <SEP><SEP>:<SEP> 6,40
<Tb>
EXAMPLE 22
In 35 ml of toluene 1.65 g (9.5 millimoles) of the methyl 3-mercapto-2-thenoate of Example 16 are dissolved and then 1.18 g (9.5 mmol) of isocyanate are added. cyclohexyl and 0.1 ml of triethylamine and refluxed for 6 hours.

 After cooling, the solution is concentrated under reduced pressure. The residual oil crystallizes by addition of a 4/1 mixture of ethyl ether and petroleum ether. The precipitate is then drained, dried and recrystallized from acetonitrile.

0.7 g of N-cyclohexyl-thiocarbamate are thus obtained.
S- (2-carbomethoxy-3-thienyl) in the form of a white powder which melts at 1730C and whose elemental analysis is in accordance with the formula C13H17NO3S2.

IR spectrum (KBr): main bands at 3320 (NH), 1680, 1630 (CO), 2920, 2860, 1440, 1270, 890 and 770 cm -1
1 H NMR (DMSO-d 6): 6H thiophene: 7.86 and 7.16; # H, NH: 5.46; NH, CH3: 3.83; 6H cyclohexyl: 3.13, 1.60 and 1.10.

EXAMPLE 23
2.78 g (0.01 mol) of 2-carbomethoxy-3-thienyl dithiocarbazate of Example 1 and 3.37 g (0.027 mol) of cyclohexyl isocyanate in 30 ml of toluene are stirred at room temperature. After stirring for 20 minutes, the abundant precipitate of bis-cyclohexylurea is filtered off and washed with 3 ml of toluene.

 To the remaining solution, 0.1 ml of triethylamine is added, followed by refluxing for 4 hours. After cooling, the solution is evaporated under reduced pressure; the residual oil crystallizes by the addition of ethyl ether. The precipitate is filtered off, washed with petroleum ether, dried and recrystallized from acetonitrile.

0.85 g of N-cyclohexyl-thiocarbamate are thus obtained.
S- (2-carbomethoxy-3-thienyl), already identified in Example 22.

EXAMPLE 24
The procedure is as in Example 23, but replacing the cyclohexyl isocyanate with 3.32 g of p-tolyl isocyanate. 1 g of N- (p.tolyl) -thiocarbamate are thus obtained.
S- (2-carbomethoxy-3-thienyl) in the form of a white powder which melts at 1540C and whose percentage analysis is in accordance with the empirical formula C14H13NO3S2.

IR spectrum (KBr): main bands at 3260 (NH), 1715, 1680 (CO), 1650, 1495, 1255, 890, 810 and 770 cm -1
1H NMR Spectrum (DMSO-d6):
Thiophenic 6H: 7.87 and 7.20; 6H tolyl: 7.20; 6H, CH3: 3.83 and 2.27; # H, NH: 10.47.

ont été préparés en opérant comme à l'exemple 22 à partir des 3-mercapto-2-thénoates des exemples 17 à 20 et/ou à partir d'autres isocyanates.EXAMPLES 25 TO 39
Other thiocarbamates of formula

were prepared by operating as in Example 22 from the 3-mercapto-2-thenoates of Examples 17 to 20 and / or from other isocyanates.

Their characteristics are summarized in the following table. The letter ag, placed after the melting point, specifies the recrystallization solvent used;
a = ethyl ether
b = acetonitrile
c = ethanol
d = 2/1 mixture of acetonitrile and ethyl ether
e = 4/1 mixture of acetonitrile and ethyl ether
f = 3/2 mixture of ether and ethyl acetate
g = 3/2 mixture of ether and hexane

<SEP> Point
<tb><SEP> EXAMPLE <SEP> R4 <SEP> R <SEP> of <SEP> fu- <SEP> Spectrum <SEP> IR (KBr) <SEP> Spectrum <SEP> of <SEP> NMR
<tb><SEP><SEP> v <SEP> cm- <SEP> (DMSO <SEP> d6)
<tb><SEP> (C)
<tb><SEP> 25 <SEP> hydrogen <SEP> phenyl <SEP> 70a <SEP> 3260 <SEP> (NH) <SEP>;<SEP> 1715, <SEP> 1650 <SEP>#H<SEP> Thiophenic: 7.30 <SEP> and <SEP> 7.93 <SEP>;
<tb><SEP> (CO) <SEP>;<SEP> 1535, <SEQ> 1435, <SEP> 1245 <SEP>#H,<SEP> CH3: 3.70 <SEP>, <SEP># H, NH: 10.80 <SEP>;
<tb><SEP> 1075 <SEP> and <SEP> 745 <SEP>#H,<SEP> C6H5: 7.30
<tb><SEP> 26 <SEP> methyl <SEP> phenyl <SEP> 142b <SEP> 3260 <SEP> (NH), <SEQ> 1710, <SEQ> 1650 <SEP> (CO) <SEP>;# H, <SEP> H5: 7.66 <SEP>;<SEP># H, NH: <SEP> 10.66 <SEP>;
<tb><SEP> 1435, <SEP> 1235, <SEP> 1100, <SEP> 880, <SEP>#H,<SEP> C6H5: 7.33; <SEP># H, CH3: 3.75 <SEP> and <SEP> 2.16
<tb><SEP> 755 <SEP> and <SEP> 690
<tb><SEP> 27 <SEP> methyl <SEP> cyclohexyl <SEP> 140b <SEP> 3300 <SEP> (NH) <SEP>;<SEP> 1710, <SEP> 1650 <SEP># H, H5: 7.46 <SEP>;<SEP># H, NH: 8.16 <SEP>;
<tb><SEP> (CO) <SEP>;<SEP> 1515, <SEQ> 1440, <SEQ> 1240 <SEP># H, CH3: 7.33 <SEP> and <SEP> 2.10 <SEP>;<SEP>#H,<SEP> cyclo
<SEP> 1110, <SEP> 830 <SEP> and <SEP> 630 <SEQ> hexyl: 3.33, <SEP> 1.63 <SEP> and <SEP> 1.13
<tb><SEP> 28 <SEP> methyl <SEP> p-tolyl <SEP> 182b <SEP> 3300 <SEP> (NH), <SEP> 1710 <SEP> and <SEP> 1665 <SEP>#H, H5: 7.60 <SEP>;<SEP>#H,<SEP> tolyl: 7.26 <SEP> and <SEP> 7.03
<tb><SEP> (CO) <SEP>;<SEP> 1510, <SEP> 1240, <SEP> 1100, <SEP># H, CH3: 3.76 <SEP> and <SEP> 2.26 <SEP>;
<tb><SEP> 820 <SEP> and <SEP> 775 <SEP># H, NH: 10.36
<tb><SEP> 29 <SEP> methyl <SEP> p-metho- <SEP> 184b <SEP> 3240 <SEP> (NH) <SEP>;<SEP> 1715 <SEP> and <SEP> 1640 <SEP># H, NH: 10.66 <SEP>;<SEP># H, H5: 7.65 <SEP>;
<tb><SEP> (CO) <SEP>;<SEP> 1500, <SEP> 1295, <SEP> 1230, <SEP># H, p.methoxyphenyl: 7.33 <SEP>;
<tb><SEP> 1100, <SEP> 1030, <SEP> 820 <SEP> and <SEP> 705 <SEP># H, CH3: 4.00, <SEP> 3.75 <SEP> and <SEP> 2.20
<tb><SEP> 30 <SEP> methyl <SEP> p-chloro- <SEP> 196b <SEP> 3300 <SEP> (NH) <SEP>;<SEP> 1710 <SEP> and <SEP> 1665 <SEP># H, H5: 7.66 <SEP>;<SEP># H, p.ClC6H4: 7.33 <SEP>;
<tb><SEP> (CO) <SEP>;<SEP> 1490, <SEP> 1235, <SEP> 1100, <SEP># H, NH: 10.66 <SEP>;<SEP># H, CH3 <SEP>: 3.75 <SEP> and <SEP> 2.16
<tb><SEP> 1010, <SEP> 825 <SEP> and <SEP> 775
<tb><SEP> 31 <SEP> methyl <SEP> 2,3-dichlo- <SEP> 125c <SEP> 3260 <SEP> (NH) <SEP>;<SEP> 1715 <SEP> and <SEP> 1650 <SEP># H, NH: 10.66 <SEP>;<SEP># H, CH3: 3.76 <SEP> and <SEP> 2.20
<tb><SEP> rophenyl <SEP> (CO) <SEP>;<SEP> 1520, <SEP> 1250, <SEP> 1110, <SEP># H, C6H3: 7.33 <SEP>;<SEP># H, H5: 7.56
<tb><SEP> 1020, <SEP> 810 <SEP> and <SEP> 705
<tb><SEP> 32 <SEP> methyl <SEP> 2,4-dichlo- <SEP> 134c <SEP> 3260 <SEP> (NH) <SEP>;<SEP> 1720 <SEP> and <SEP> 1650 <SEP># H, N: 10.16 <SEP>;<SEP># H, H5: 7.60 <SEP>;
<tb><SEP> (CO) <SEP>;<SEP> 1505, <SEP> 1260, <SEP> 1110, <SEP># H, C6H3: 7.40 <SEP>;<SEP># H, CH3: 3.73 <SEP> and
<tb><SEP> 820 <SEP> and <SEP> 760 <SEP> 2.30
<Tb>

<SEP> Point
<tb><SEP> EXAMPLE <SEP> R4 <SEP> R <SEP> of <SEP> fu- <SEP> Spectrum <SEP> IR (KBr) <SEP> Spectrum <SEP> of <SEP> NMR
<tb><SEP><SEP> v <SEP> cm- <SEP> (DMSO <SEP> d6)
<tb><SEP> (C)
<tb><SEP> 33 <SEP> methyl <SEP> 3,4-dichlo- <SEP> 186c <SEP> 3240 <SEP> (NH) <SEP>;<SEP> 1715 <SEP> and <SEP> 1660 <SEP>#H,<SEP> NH: 10.76 <SEP>;<SEP># H, H5: 7.56 <SEP>;
<tb><SEP> rophenyl <SEP> (CO) <SEP>, <SEQ> 1445, <SEP> 1250, <SEQ> 1115, <SEP>#H<SEP> CH3: 3.73 <SEP> and <SEP> 2.20 <SEP>;
<tb><SEP> 1025, <SEP> 830 <SEP> and <SEP> 780 <SEP># H, C6H3: 7.63 <SEP> and <SEP> 7.33
<tb><SEP> 34 <SEP> methyl <SEP> p.nitro- <SEP> 187b <SEP> 3295 <SEP> (NH) <SEP>;<SEP> 1720 <SEP> and <SEP> 1675 <SEP># H, NH: 11.06 <SEP>;<SEP># H, H5: 7.56 <SEP>;
<tb><SEP> phenyl <SEP> (CO) <SEP>;<SEP> 1495, <SEQ> 1330, <SEQ> 1145, <SEP># H, p, O2NC6H4: 8.06 <SEP> and <SEP> 7.56 <SEP>;
<tb><SEP> 1010, <SEP> 810 <SEP> and <SEP> 750 <SEP># H, CH3: 3.75 <SEP> and <SEP> 2.15
<tb><SEP> 35 <SEP> phenyl <SEP> benzyl <SEP> 148d <SEP> 3360 <SEP> (NH) <SEP>;<SEP> 1710 <SEP> and <SEP> 1670 <SEP># H, NH: 8.66 <SEP>;<SEP># H, H5: 7.83 <SEP>;
<tb><SEP> (CO) <SEP>;<SEP> 1480, <SEP> 1235, <SEP> 1070, <SEP># H, C6H5: 7.26 <SEP> and <SEP>7.06;# H, CH2: 4.20;
<tb><SEP> 925, <SEP> 790 <SEP> and <SEP> 695 <SEP># H, CH3: 3.73
<tb><SEP> 36 <SEP> phenyl <SEP> phenyl <SEP> 134th <SEP> 3280 <SEP> (NH) <SEP>;<SEP> 1715 <SEP> and <SEP> 1660 <SEP># H, NH: 10.40 <SEP>;<SEP># H, H5: 7.80 <SEP>;
<tb><SEP> (CO) <SEP>;<SEP> 1435, <SEP> 1235, <SEP> 1070, <SEP># H, C6H5: 7.24 <SEP> and <SEP> 7.05 <SEP>;<SEP># H, CH3: 3.72
<tb><SEP> 750 <SEP> and <SEP> 700
<tb><SEP> 37 <SEP> p.chloro- <SEP> cyclohexyl <SEP> 144b <SEP> 3270 <SEP> (NH) <SEP>;<SEP> 1725 <SEP> and <SEP># H, NH: 8.03 <SEP>;<SEP># H, C6H4: 7.36 <SEP>;
<tb><SEP> phenyl <SEP> 1665 <SEP> (CO) <SEP># H, H5: 7.83 <SEP>;<SEP># H, CH3: 3.73 <SEP>;
<p>SEP> 38 <SEP> p.fluoro- <SEP> cyclohexyl <SEP> 124f <SEP> 3280 <SEP> (NH) <SEP>;<SEP> 1725 <SEP> and <SEP>#H, C6H11: 1.56 <SEP> and <SEP> 1.13
<tb><SEP> 1660 <SEP> (CO)
<tb><SEP> 39 <SEP> p.bromo- <SEP> cyclohexyl <SEP> 158b <SEP> 3280 <SEP> (NH) <SEP>;<SEP> 1725 <SEP> and <SEP>#H,<SEP> NH: 8.10 <SEP>;<SEP># H, H5: 7.85 <SEP>;
<tb><SEP> 1660 <SEP> (CO) <SEP># H, C6H4: 7.53 <SEP> and <SEP> 7.26 <SEP>;<SEP># H, CH3: 3.80;
<tb><SEP>#H,<SEP> C6H11: 1.60 <SEP> and <SEP> 1.16
<Tb>
EXAMPLE 40
2.171 g (0.005 mol) of 2-carbomethoxy-5- (4-fluorophenyl) -3-thienyl dithiocarbazate of Example 11 are stirred for 2 minutes in 100 ml of a 10% hydrochloric acid solution. The solution is then extracted with 150 ml of ethyl ether and the ethereal phase is washed with 100 ml of water, then dried and concentrated under reduced pressure at 400C.

 The residual oil obtained, consisting of methyl 3-mercapto-5 (4-fluorophenyl) -2-thenenoate (1 g), is dissolved in 35 ml of toluene. 0.46 g of cyclohexyl isocyanate and 0.1 ml of triethylamine are then added and the solution is refluxed for 6 hours. After cooling, the solution is concentrated under reduced pressure. The residual oil crystallizes by addition of a 4/1 mixture of ethyl ether and petroleum ether. The precipitate is then drained, dried and recrystallized from acetonitrile.

0.45 g of N-cyclohexyl-thiocarbamate are thus obtained.
S- [2-carbomethoxy-5- (4-fluorophenyl) -3-thienyl] as a white powder which melts at 1690C and whose elemental analysis is according to the empirical formula C19H20NO3S2F.

IR spectrum (KBr): main bands at 3280 (NH), 1700 and 1650 (CO), 1450, 1230, 1210, 1090, 825, 760 and 710 cm -1
1H NMR Spectrum (DMSO-d6)
6H, NH: 8.36; NH, FC6H4 and H4: 7.70 and 7.20; NH, CH3 3.80; 6H, cyclohexyl: 3.60, 1.70 and 1.23.

EXAMPLE 41
The procedure is as in Example 40 but replacing the dithiocarbazate of Example 11 with that of Example 14. To 2.88 g (0.01 mol) of this compound is used 0.99 g of isocyanate cyclohexyl.

sous forme d'une poudre blanche qui fond à 192 C.0.4 g of the thiocarbamate of formula

in the form of a white powder which melts at 192 C.

IR spectrum (KBr): main bands at 3320 (NH), 1710 and 1655 (CO), 1435, 1310, 1225, 1080, 830 and 760 cm -1
1H NMR Spectrum (DMSO-d6)
# H, NH: 8.30; # H, CH3: 3.76; 6H, cyclohexyl: 1.66 and 1.20; #H, heterocycle: 2.93 and 2.50
EXAMPLE 42
0.5 g of the methyl 3-mercapto-4-methyl-2-thenenoate described in Example 17 and 0.35 g of phenylisothiocyanate in 40 ml of toluene are refluxed for 4 hours in the presence of 0.05 g. ml of triethylamine.

After cooling, the solution is concentrated under reduced pressure and the residue obtained is recrystallized from ethanol. There is thus obtained 0.6 g of 2-carbomethoxy-4-methyl-3-thienyl N-phenyl-dithiocarbamate in the form of a yellow powder which melts at 8 ° C. and whose elemental analysis is in accordance with the empirical formula C 14 H 13 NO 2 S 3
IR spectrum (KBr): main bands at 3100 (NH), 1715 (CO), 1445, 1330, 1225, 1100, 780 and 760 cm -1
1H NMR Spectrum (DMSO-d6):
6H, H5: 7.30; # H, NH: 11.00; NH, C6H5: 7.43; NH, CH3, 3.73 and 2.13.

dont les caractéristiques figurent dans le tableau suivant

EXAMPLES 43 TO 50
The procedure is as in Example 40 but replacing the dithiocarbazate of Example 11 with the 2-carbomethoxy-3-benzo [b] thienyl dithiocarbazate of Example 4. From 2.98 g (0.01 mole) of this compound and using 0.0097 moles of different isocyanates, the corresponding thiocarbamates of formula

whose characteristics are shown in the following table

<tb> Point <SEP>
<tb><SEP> EX <SEP> R <SEP> of <SEP> Spectrum <SEP> IR (KBr) <SEP> Spectrum <SEP> NMR1H
<tb><SEP> Merge <SEP> v <SEP> cm <SEP> 1 <SEP> (DMSO <SEP> d6)
<tb><SEP> (C)
<tb><SEP> 3300 <SEP> (NH) <SEP>;<SEP> 1715 <SEP> and <SEP># H, NH: 8.40 <SEP><SEP>;<SEP>#H,<SEP> CH3
<tb><SEP> 43 <SEP> isopropyl <SEP> 178b <SEQ> 1655 <SEP> (CO) <SEP>;<SEP> 1490, <SEP> 3.86 <SEP> and <SEP> 1.13 <SEP>;<September>
<tb><SEP> 1230, <SEP> 1210, <SEP> 800 <SEP> and <SEP> EH, <SEP> Benzothiophene
<tb><SEP> 760 <SEP> 7.93 <SEP> and <SEP> 7.50
<tb><SEP> 3240 <SEP> (NH) <SEP>;<SEP> 1710 <SEP> and <SEP>"# H, NH: 10.66 <SEP>;# H, CH3 <SEP>
<tb><SEP> 44 <SEP> phenyl <SEP> 116g <SEP> 1650 <SE> (CO) <SEP>;<SEP> 1490, <SEP> 3.83 <SEP>;<SEP> 6H, C6H5: 7.40;
<tb><SEP> 1225, <SEP> 1160, <SEP> 1090 <SEP> and <SEP> 6H, benzothiophene: <SEP>
<tb><SEP> 750 <SEP> 8.00 <SEP> and <SEP> 7.40
<tb><SEP> 3305 <SEP> (NH) <SEP>;<SEP> 1700 <SEP> and <SEP> bH, NH: 9.00; 6H, CgHg: <SEP>
<tb><SEP> 1670 <SEP> (CO) <SEP>;<SEP> 1490, <SEP> 7.30 <SEP>;<SEP># H, benzothio- <SEP>
<tb><SEP> 45 <SEP> benzyl <SEP> 138a <SEP> 1230, <SEQ> 1195, <SEP> 1090, <SEP> phene: 8.00 <SEP> and <SEP> 7.50 <SEP >
<tb><SEP> 870 <SEP> and <SEP> 750 <SEP> 6H, CH2: 3.92 <SEP>;
<tb><SEP> NH, CH3: 3.83 <SEP>
<tb><SEP> 3320 <SEP> (NH) <SEP>;<SEP> 1690 <SEP> and <SEP> EH, NH: 9.00 <SEP>; 6H, C6H5:
<tb><SEP> 46 <SEP>&alpha; -methyl- | <SEP><SEP> 130a <SEP> 1660 <SEP> (CO) <SEP>;<SEP> 1490, <SEP> 7.20 <SEP>;<SEP> 6H, CH: 4.76 <SEP>;<September>
<tb><SEP> benzyl <SEP> 1280, <SEP> 1215, <SEP> 840 <SEP> and <SEP> 6H, CH3: 3.73 <SEP> and <SEP>1.36;
<tb><SEP> 700 <SEP> 6H, benzothiophene:
<tb><SEP> 7.96, <SEP> 7.66 <SEP> and <SEP> 7.40
<tb><SEP> 3310 <SEP> (NH) <SEP>;<SEP> 1725 <SEP> and <SEP># H, NH: 8.33; # H, C6H11: <SEP>
<tb><SEP> 47 <SEP> cyclo- <SEP> 138a <SEP> 1755 <SEP> (CO) <SEP>;<SEP> 2940, <SEP> 3.40, <SEP> 1.66 <SEP> and <SEP> 1.20 <SEP>;
<tb><SEP> hexyl <SEP> 2860, <SEP> 1500, <SEP> 1230, <SEP># H, CH3: 3.76 <SEP><SEP>;<SEP> 6H,
<tb><SEP> 1090, <SEP> 840 <SEP> and <SEP> 755 <SEP> Benzothiophene: 8.00, <SEP>
<tb><SEP> 7.80 <SEP> and <SEP> 7.43
<tb><SEP> 3305 <SEP> (NH) <SEP>;<SEP> 1715 <SEP> and <SEP># H, NH: 10.80; # H, CH3: <SEP>
<tb><SEP> 1670 <SEP> (CO) <SEP>;<SEP> 1515, <SEP> 3.84 <SEP> and <SEP> 2.26 <SEP>;<SEP> 6H,
<tb><SEP> 48 <SEP> p.tolyl <SEP> 170b <SEP> 1440, <SEP> 1240, <SEP> 1100, <SEP> benzothiophene: 8.00 <SEP>
<tb><SEP> 820 <SEP> and <SEP> 770 <SEP> and <SEP> 7.50 <SEP>;<SEP> 6H, tolyl: <SEP>
<tb><SEP> 7.26
<tb><SEP> 3240 <SEP> (NH) <SEP>;<SEP> 1720 <SEP> and <SEP> 6H, NH: 10.83; 6H, CH3: <SEP>
<tb><SEP> 49 <SEP> 4-chloro- | <SEP> 182b <SEP> 1655 <SEP> (CO) <SEP>;<SEP> 1590, <SEP> 3.86 <SEP>;<SEP> SH, C6H4: 7.50 <SEP>
<tb><SEP> phenyl <SEP> 1480, <SEP> 1220, <SEP> 1010, <SEP> and <SEP> 7.33 <SEP>;<SEP> 6H, benzo- <SEP>
<tb><SEP> 815 <SEP> and <SEP> 730 <SEP> Thiophene: 8.00 <SEP> and
<tb><SEP> 7.50
<tb><SEP> 3270 <SEP> (NH) <SEP>;<SEP> 1720 <SEP> and <SEP> 6H, NH: 11.04; <SEP> NH, CH3: <SEP>
<tb><SEP> 50 <SEP> 4-nitro- <SEP> 218b <SEP> 1670 <SEP> (CO) <SEP>;<SEP> 1490, <SEP> 3.80 <SEP>;<SEP> 6H, nitrophene - <SEP>
<tb><SEP> phenyl <SEP> 1330, <SE> 1230, <SE> 1110, <SEP> nyl <SEP> and <SEP> benzothiophene
<tb><SEP> 805-and <SEP> 750 <SEP> ne: 8.06, <SEP> 7.56, <SEP> 8.00
<tb><SEP> and <SEP> 7.50
<Tb>
EXAMPLE 51
0.5 g (0.002 mol) of the 2-carbomethoxy-3-thienyl dithiocarbazate of Example 1 are stirred at room temperature in 10 ml of acetic anhydride. The precipitate of diacetylhydrazine formed in 5 minutes is drained and washed with ethyl ether, then the remaining solution is heated for 10 minutes at 800C and then poured with stirring into a saturated solution of potassium hydrogencarbonate.After one hour of stirring the solution is extracted with 150 ml of ethyl ether, washed with water and dried, and then concentrated under reduced pressure. The residual oil precipitates as light yellow crystals which are recrystallized from ethyl ether.

 There is thus obtained 0.42 g of S- (2-carbomethoxy-3-thienyl) thioacetate which melts at 68 ° C. and whose elemental analysis is in accordance with the empirical formula C 8 H 8 O 3 S 2.

IR spectrum (KBr): 1690 cm- (CO)
1H NMR Spectrum (DMSO d6)
# H4: 7.30; # H5: 7.90; 6CO2CH3: 3.80; # COCH3: 2.43
EXAMPLE 52
The procedure is as in Example 51, but replacing the dithiocarbazate of Example 1 with 2-carbomethoxy-4-methyl-3thienyl dithiocarbazate of Example 2.

S- (2-carbomethoxy-4-methyl-3-thienyl) thioa ketate, which melts at 600 ° C. and whose elemental analysis is in accordance with the empirical formula CgH1003S2, is thus obtained in the form of orange crystals.
Spectrum II (KBr): Main bands at 3110, 2960, 1690 (CO), 1435, 1355, 1015, 945 and 795 cm 1
1H NMR Spectrum (DMSO d6)
6H5: 7.70; SCO2CH3: 3.80; SCH3 (4): 2.17; # COCH3: 2.43
EXAMPLE 53
The procedure is as in Example 51, but replacing the acetic anhydride with 15 ml of butyric anhydride. 0.4 g of S- (2-carbomethoxy-3-thenyl) thiobutyrate is obtained in the form of a dark yellow oil.

IR spectrum (KBr): Main bands at 2920, 1690, 1480, 1420, 1385, 1230, 1155, 950, 875 and 750 cm -1
1H NMR Spectrum (DMSO d6)
6H4: 7.23; H5: 7.90; # CO2CH3: 3.70; SCH2: 1.57 and 2.57; # CH3: 0.83
EXAMPLE 54
0.5 g of methyl 3-mercapto-2-ethenoate in 60 ml of dichloromethane are stirred at ambient temperature. 0.5 g of potassium carbonate and 1 ml of water are added to the solution, followed by 2 ml of methyl iodide. The mixture is then refluxed for one hour and a half, then the solution is evaporated under reduced pressure and the residue is taken up in water and then extracted with ether. The ether phase is dried and then concentrated to dryness and the crystals obtained are recrystallized from ethyl ether.

 There is thus obtained 0.27 g of methyl 3-methylthio-2-thenenoate which melts at 1220C.

IR spectrum (KBr): Main bands at 3090, 1685, 1490, 1435, 1400, 1255, 1075, 890 and 765 cm -1
1H NMR Spectrum (DMSO d6)
6H4: 7.10; 6H5: 7.83; ECO2CH3: 3.80; 6CH3: 2.53
EXAMPLE 55
0.5 g of methyl 3-mercapto-2thenoate and 0.23 g of 2-chloroethanol in 40 ml of dichloromethane and 1 ml of water are stirred at ambient temperature. 1.78 g of sodium carbonate are added to the solution and the resulting mixture is refluxed for 2 hours. After cooling, the solution is concentrated under reduced pressure. The residue is taken up in water, acidified with 10% hydrochloric acid and then extracted with ether, dried over magnesium sulfate and concentrated under reduced pressure. The residue is then recrystallized from ethyl ether.

 0.3 g of 3- (2-hydroxyethylthio) -2-thonic acid is obtained in the form of a white solid which melts at 15 ° C. and whose elemental analysis corresponds to the empirical formula C 7 H 8 O 3 S 2.

IR spectrum (KBr): Main bands at 3570, 3070, 2930, 2600, 1655, 1485, 1425, 1265, 1050, 890 and 765 cm -1
1H NMR Spectrum (DMSO d6)
6H4: 7.03; 6H5: 7.70; SOH: 6.20; SCH2: 3.00 and 3.50
EXAMPLE 56
0.7 g (0.0028 mol) of 2-carbomethoxy-3-thienyl dithiocarbazate are stirred at room temperature in 10 ml of methylene chloride and then 1.38 g of benzoyl chloride are added dropwise. A precipitate is immediately formed which is filtered off and then washed with 15 ml of dichloromethane.

 The remaining solution is then heated for 3 hours before evaporating the dichloromethane. The residue is taken up in water and then extracted with ether and the ether phase is concentrated in vacuo. The residual oil crystallizes.

 After recrystallization from petroleum ether, 0.13 g of S- (2-carbomethoxy-3-thienyl) thiobenzoate, which melts at 58 ° C., is obtained.

IR spectrum (KBr): Main bands at 1715, 1660, 1435, 1405, 1245, 1205, 1100, 1075, 895, 775 and 690 cm -1
1H NMR Spectrum (DMSO d6)
H4: 7.33; 6H5: 7.96; ECO2CH3: 3.73; & 6H5: 7.50
EXAMPLE 57
0.38 g (0.002 mol) of methyl 3-mercapto-4-methyl-2-thenenoate in 100 ml of dichloromethane are stirred at room temperature, then 0.16 g of pyridine and 0.38 g of tosyl chloride are added.

 The mixture is refluxed for 2 hours. The solution is then evaporated and taken up in water, washed with dilute hydrochloric acid and then with water and extracted with ether. The ether phase is washed with water, decanted, dried over magnesium sulphate and then evaporated under reduced pressure.

The yellow oil crystallizes.

0.23 g of S (2-carbomethoxy-4-methyl-3-thienyl) p-toluenethiosulphonate, which melts at 500 ° C. and whose elemental analysis is in accordance with the empirical formula C14H144S3-
IR spectrum (KBr): Main bands at 3100, 2960, 1720, 1700, 1595, 1440, 1375, 1280, 1230, 1175, 1100, 1015, 810, 780 and 655 cm -1
1H NMR Spectrum (DMSO d6)
6H5: 7.56; EC6H4: 7.47 and 7.13; 6CO2CH3: 3.67 6CH3: 2.23
EXAMPLE 58
Refluxed for 2 hours, 0.5 g of methyl 3-mercapto-4-methyl-2-thenenoate and 0.28 g of ethyl chloroformate in 40 ml of dichloromethane in the presence of 0.5 g of triethylamine. After cooling the resulting solution is concentrated under reduced pressure, then taken up in water, extracted with ether, dried over magnesium sulphate and concentrated under reduced pressure.

 There is thus obtained 0.26 g of a yellow oil consisting of 0-ethyl thiocarbonate and S- (2-carbomethoxy-4-methyl-3-thienyl).

IR spectrum (KBr): Main bands at 3100, 3000, 2960, 1710 (broad), 1440, 1250, 1140, 1095, 1015, 850 and 780 cm -1
1H NMR Spectrum (DMSO d6)
H, 7.63; 6CO2CH3: 3.77; 6CH2: 4.17; 6CH3: 1.20; SCH3 (4): 2.20
EXAMPLE 59
0.2 g of methyl 3-mercapto-4-methyl-2-thenenoate in 10 ml of toluene are stirred at ambient temperature, and 10 ml of phosgene in 20% solution in toluene are then added.

The mixture is then refluxed for 2 hours. After cooling, the solution is concentrated under reduced pressure and the yellow crystals formed are recrystallized from a 50/50 ether / hexane mixture.

qui fond à 80"C. 0.16 g of the dithiocarbonate of formula

which melts at 80 "C.

IR spectrum (KBr): Main bands at 3430, 3095, 2950, 2920, 1715, 1440, 1230, 1095, 1015, 865, 820 and 780 cm 1
1H NMR Spectrum (DMSO d6)
SH5: 7.56; 6CO2CH3: 3.56; SCH3 (4): 2.10
EXAMPLE 60
0.5 g (0.003 mol) of methyl 3-mercapto-4-methyl-2-thenenoate are stirred at room temperature in 100 ml of dichloromethane, and then 0.62 g of triethylamine and 0.19 g (0.0015 g) are added. mole) of oxalyl chloride.

 The mixture is refluxed for 2 hours. The solution is then evaporated and taken up in water and extracted with ether. The ether phase is washed with water, decanted, dried over magnesium sulfate and then evaporated under reduced pressure.

sous forme de cristaux jaunes qui fondent à 2280C.0.58 g of the dithiooxalate of formula

in the form of yellow crystals which melt at 2280C.

IR spectrum (KBr): Main bands at 3110, 2960, 1720, 1680, 1440, 1245, 1305, 1015 and 775 cm -1
1H NMR Spectrum (DMSO d6)
6H5: 7.80; SCO2CH3: 3.83; 6CH3 (4): 2.20
EXAMPLE 61
By operating as in Example 60, starting from 0.7 g of methyl 3-mercapto-4-methyl-2-thenothate, 0.81 g of triethylamine and 0.45 g of chloroacetyl chloride, 0.65 is obtained. g of S- (2-carbomethoxy-4-methyl-3-thienyl) chlorothioacetate in the form of a beige powder which melts at 940C and whose elemental analysis is in accordance with the empirical formula
C9H9O3S2Cl.

IR spectrum (KBr): Main bands at 1710 (CO), 1445, 1250, 1000, 800 and 740 cm 1
1H NMR Spectrum (DMSO d6)
6H5: 7.66; CH 2: 4.70; SCO2CH3: 3.76; 6CH3 (4): 2.13
EXAMPLE 62
To a mixture of 3 g of the compound of the preceding example in 60 ml of dimethylformamide is added 0.8 g of butylamine and 1.16 g of sodium carbonate and the mixture is heated at 1300C for 2 hours.

 After cooling, the solution is poured into water and then extracted with 200 ml of ethyl ether. After recrystallization from a 4/1 ether / hexane mixture, 2.75 g of S- (2-carbomethoxy-4-methyl-3-thienyl) butylamino-thioacetate are obtained, which melts at 660 ° C. and the elemental analysis of which is consistent with with the empirical formula C13H19NO3S2.

IR spectrum (KBr): 3300 (NH); 1710 and 1650 (CO)
1H NMR Spectrum (DMSO d6)
#NH: 7.73; 6H5: 7.53; 6CO2CH3: 3.76; 6CH3 (4) 2.20; 6CH2: 2.93 and 1.16; SCH3: 0.83
By passing a stream of gaseous hydrochloric acid in a solution of this compound in anhydrous ether, its hydrochloride is obtained in the form of a yellow powder which melts at 430C.

IR spectrum (KBr): 3300, 2960, 2880, 1550 (NH +), 1710 and 1650 (CO)
1H NMR Spectrum (DMSO d6)
6H5: 7.50; 6NH +: 4.96; ECO2CH3: 3.80; SCH2: 2.93, 1.26 and 1.06; SCH3: 0.80; 8CH3 (4): 2.26
EXAMPLES 63 TO 70
0.7 g (0.004 mol) of methyl 3-mercapto-4-methyl-2-thenenoate are stirred at ambient temperature in 100 ml of dichloromethane, and 0.81 g (0.008 mol) of triethylamine and 0.62 g are then added ( 0.004 moles) of 5-chlorovaleryl chloride.

 The mixture is refluxed for 2 hours. The solution is then evaporated and taken up in water and extracted with ether. The ether phase is washed with water, decanted, dried over magnesium sulphate and then evaporated under reduced pressure.

 0.24 g of S (2-carbomethoxy-4-methyl-3-thienyl) 5-chloropentanethioate are thus obtained in the form of a red oil.

qui se présentent tous sous forme d'huiles et dont les caractéristiques sont rassemblées dans le tableau suivant.

IR spectrum (KBr): Main bands at 3100, 2980, 1720, 1450, 1350, 1235, 1105, 1015, 870, 825 and 775 cm 1
1H NMR Spectrum (DMSO d6)
H, 7.67; 6CO2CH3: 3.73; 6CH3 (4): 2.23; 6CH2 3.60, 2.70 and 1.67
By operating in the same way with acid chlorides and corresponding 3-mercapto-2-thenoates, different compounds of formula

all of which are in the form of oils and whose characteristics are summarized in the following table.

<SEP> Eb.
<Tb>

<SEP> EX. <SEP> R4 <SEP> R5 <SEP> n <SEP> R4 <SEP> (C) <SEP> Spectrum <SEP> IR (KBr) <SEP> Spectrum <SEP> of <SEP> NMR <SEP> 1H
<tb><SEP> under <SEP> (DMSO <SEP> d6)
<tb><SEP> 667 <SEP> v <SEP> cm-
<tb><SEP> Pa
<tb><SEP> 3100, <SEP> 2960, <SEP> 2520, <SEP> 1740 <SEP># H5: 7.70 <SEP>;<SEP># CO2CH3: 3.87 <SEP>;
<tb><SEP> 64 <SEP> CH3 <SEP> H <SEP> 1 <SEP> C2H5 <SEP> 130 <SEP> (large), <SEP> 1530, <SEQ> 1450, <SEQ> 1240, <SEP># CH3: 2.17 <SEP>;<SEP># CH2: 4.13 <SEP>;
<tb><SEP> 1110, <SEP> 1015, <SEP> 920, <SEP> 870, <SEP># CH3: 1.23
<tb><SEP> 780 <SEP> and <SEP> 655
<tb><SEP> 3,4-di- <SEP> 1740, <SEP> 1720, <SEP> 1700 <SEP> (CO) <SEP># H5: 7.26 <SEP>;<SEP># C6H3: 7.43 <SEP> and <SEP> 7.00
<tb><SEP> 65 <SEP> CH3 <SEP> H <SEP> 2 <SEP> chloro- <SEP> 160 <SEP># CH2: 4.83, <SEP> 2.80 <SEP> and <SEP > 2.50 <SEP>;
<tb><SEP> benzyl <SEP># CO2CH3: 3.56 <SEP>;<SEP># CH3: 1.93
<tb><SEP> 1740, <SEQ> 1720, <SEQ> 1700 <SEP> (CO) <SEP># H5: 7.56 <SEP>;<SEP># CH2: 3.96, <SEP> 2.60
<tb><SEP> 66 <SEP> CH3 <SEP> H <SEP> 2 <SEP> octyl <SEP> 150 <SEP> and <SEP> 1.33 <SEP>;<SEP># CO2CH3: 3.60 <SEP>;
<tb><SEP># CH3: 0.86
<tb><SEP># CH2: 3.93, <SEP> 2.86, <SEP> 1.46 <SEP> and <SEP> 1.23
<tb><SEP> 67 <SEP> CH3 <SEP> CH3 <SEP> 2 <SEP> octyl <SEP> 170 <SEQ> 1720, <SEQ> 1700 <SEP> (CO) <SEP># CO2CH3: 3, 70 <SEP>;<SEP># CH3 (4 <SEP>& 5): 2.33
<tb><SEP># CH3: 0.80
<tb><SEP>#H,<SEP> Benzothiophene: 7.96, <SEP> 7.73
<sep> 68 <SEP> -CH-CH-CH = CH- <SEP> 2 <SEP> octyl <SEP> 160 <SEP> 1720, <SEQ> 1700 <SE> (CO) <SEP> and <SEP> 7.40 <SEP>;<SEP># CH2: 3.90, <SEP> 3.00,
<tb><SEP> 2.50, <SEP> 1.43 <SEP> and <SEP> 1.10 <SEP>;
<tb><SEP># CO2CH3: 3.76 <SEP>;<SEP># CH3: 0.76
<tb><SEP>#H,<SEP> benzothiophene: 8.00, <SEP> 7.73
<sep> 69 <SEP> -CH = CH-CH = CH- <SEP> 4 <SEP> CH3 <SEP> 165 <SEQ> 1740, <SEQ> 1720, <SEQ> 1700 <SEP> (CO ) <SEP> and <SEP> 7.46 <SEP>;<SEP># CO2CH3: 3.80 <SEP>;
<tb><SEP># CH3: 1,10 <SEP>;<SEP># CH2: 2.76, <SEP> 2.30
<tb><SEP> and <SEP> 1.56
<tb><SEP># CO2CH3: 3.73 <SEP>;<SEP># CH3: 0.86 <SEP>;
<tb><SEP> 70 <SEP> -CH2CH2CH2CH2- <SEP> 2 <SEP> Octyl <SEP> 170 <SEQ> 1740, <SEQ> 1720, <SEQ> 1700 <SEP> (CO) <SEP># CH2 : 4.00, <SEP> 3.30, <SEP> 2.70, <SEP> 1.66 <SEP>, and
<tb><SEP> 1.26
<Tb>

Claims (11)

 is a number from 0 to 4.  if m = 2, R3 represents a bridge -CO- or -CO (CH2) nCO- where n  substituted, phenyl or tolyl;  represents a C1 to C4 alkyl radical  represents a C1 to C8 alkyl radical and R "  optionally substituted heterocyclic, R '  tick, arylaliphatic, aromatic or  represents an aliphatic, cycloalipha radical  -COOR ', acyl -COR "or sulfonyl -SO2R", where R  average -CONHR, thiocarbamoyl -CS-NHR, ester  a thiocarbazoyl group -CS-NHNH2, carba  optionally substituted C1-C4 alkyl or  if m = l, R3 represents a hydrogen atom, a radical  -CH = CH-CH = CH- or C3-C5 alkylene;  substituted, or together form a concatenation  or a heterocyclic radical  C4, an optionally substituted phenyl radical  a hydrogen atom, an alkyl radical C1 to  R4 and R5, identical or different, represent each  R2 represents a C1 to C20 alkyl radical;  m is 1 or 2  in which

 1. The thiophenic compounds of general formula  2. Compounds according to claim 1, wherein R2 is a methyl radical.  3. Process for preparing the dithiocarbazates of the general formula

 in which R2, R4 and R5 have the same meanings as in claim 1, characterized in that it consists in reacting the hydrazine with O-alkyl dithiocarbonate and S- (2-carbalcoxy-3-thienyl) ), obtained by reaction of the corresponding 3-amino-2-thenoate diazonium salt of formula

 with an alkali metal alkylxanthate MS-CS-OQ where M is sodium or potassium and Q is methyl, ethyl or propyl.  4. The method of claim 3, wherein the molar ratio hydrazine / dithiocarbonate is between 1 and 3, and preferably between 1.3 and 2.  5. Method according to claim 3 or 4, wherein one operates in an inert solvent at a temperature ranging from -10 to +400C, preferably at room temperature.  6. Method according to one of claims 3 to 5, wherein the hydrazine hydrate is used.  7. Process for preparing the thiols of the general formula

 wherein R2, R4 and R5 have the same meanings as in claim 1, characterized by treating the corresponding dithiocarbazate (I-a) with an acidic medium.  8. Process according to claim 7, in which the reaction is carried out at ambient temperature using a quantity of 10% aqueous hydrochloric acid solution which is sufficient to obtain the complete dissolution of the dithiocarbazate and a quantity of ethyl ether or dithiocarbazate. ethyl acetate sufficient to extract the released thiol.  9. Process for the preparation of compounds (I) in which m is equal to 1 and R3 is optionally substituted alkyl radical or a carbamoyl, thiocarbamoyl, ester, acyl or sulphonyl group, characterized in that a thiol (I- b) with a haloalkane, an isocyanate or isothiocyanate, an alkyl chloroformate, or an anhydride or acid halide.  10. Process for the preparation of compounds (I) in which m is equal to 2, characterized in that a thiol (I-b) is reacted with phosgene or a diacid dichloride.  The process according to claim 9 or 10, wherein the reaction is carried out under reflux in an inert solvent.