DD200618A1 - PROCESS FOR THE PREPARATION OF NEW N-AROYL AND HETAROYLIMIDES - Google Patents

Abstract

The invention relates to a synthesis for the preparation of N-aroyl and Hetaroylimiden of the general formula I, in which R is an aryl, optionally substituted on the phenyl nucleus aryl group; Phenylvinyl, optionally substituted on the phenyl nucleus; Furylvinyl-; pyridyl; Thienyl group and R & exp1 !, R & exp2! a mercapto, methylthio, C & ind2! -C & ind5! alkylthio; C & ind1 -C IND5 alkylamino-!; Arylamino, optionally substituted on the phenyl nucleus or one or more times by halogens substituted aryl group; Benzylamino and cyclohexylamino mean. The aim of the invention is to produce new substituted N-aroyl and Hetaroylimide in a simple manner. According to the invention aroyl or Hetaroylamide be reacted with isothiocyanates to (iso) thioureas and with carbodiimides to N-aroyl and Hetaroylguaniden under simple reaction conditions. N-Aroyl and Hetaroylimide are important as possible products for the production of Schaedlingbekaempfungsmitteln. (Formula)

Description

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Title of the invention

for the preparation of novel N-aroyl and Hetaroylimiden

Fields of application of the invention

The invention relates to a process for the preparation of novel substituted N-aroyl and Hetaroylimiden of the general formula I, in which R is an aryl, optionally substituted on the phenyl nucleus aryl group; Phenylvinyl, optionally substituted on the hienyl nucleus; Purylvinyl-; pyridyl; thienyl

12 and R, R is a mercapto; methylthio; Cp C ^ alkylthio,

-, Arylamino-, optionally on the phenyl nucleus

one or more halo-substituted aryl group; Benzylamino and cyclohexylamino mean.

It is known that some substituted (iso) thioureas, e.g. the N- (2,6-dichlorobenzoyl) -N '(3,4-dichlorophenyl) thiourea and others which are insecticidally effective, and whose copper compounds have fungicidal and bactericidal properties, are used as pesticides and substituted phenylguanidines as antihypertensive agents.

Characteristic of the known technical solutions

So far, only substituted N-phenyl-N ^f -benzoyl-thioureas and substituted N-phenyl-N'-alkylaryl-iso (thio) ureas of the formula III are known (see US Patent 3393 908, DDR-WP 74262, BRD patent No. 2901 091, Federal Republic of Germany Patent 2837 086 and Federal Republic of Germany Patent 2608 488), which have been obtained according to known methods by reacting substituted anilines with a halide,

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Phenylisothiocyanates in the presence of a base with cyanamide or with chloromethanesulfonamide, isothioureas with substituted isocyanates, or Iminodithiokohlensäureester with sulfonyl chloride (see Chm.Ber. £ 2., ²⁸⁸ 5 (1966); Angw. Chemie 22 »549 (1965) and Chem.Ber. 9.2, 1252 (1966)) in imiddichlorides (see Ang. Chemistry 22 »430, 549 (1965); Tetrahedron Lett. (1965), 1753 and Chem. Ber. 99, 1252 (1966)) and then reacted with substituted anilines ,

There are substituted N-phenylguanidines of the formula IV (see US-Batent 3914 306, BRD Patent 2516 936) are known, which are prepared by condensation of cyanamides and substituted anilines.

Disadvantages of these methods are that the iso (thio) ureas are often formed only after prolonged reaction times at temperatures of 0 to 1GO C and partly under elevated pressure. It is only multi-step process, wherein in the presence of acid-binding agents or bases such. Amines, hydroxides, carbamates or alkali metals, e.g. Potassium t-butylate is worked.

In addition, the previously proposed methods for the carboxylic acid amides used by us as starting materials for (iso) thioureas and guanidines of the formulas III and IV are not applicable.

Object of the invention

The aim of the invention are novel substituted N-aroyl and Hetaroylimide.

Explanation of the essence of the invention

The Erindung is the object to produce substituted N-aroyl and Hetaroylimide after a simple process.

According to the invention substituted N-aroyl and Hetaroylimide the general formula

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RC ₁ -N = C II

in which

R is aryl, hetaroyl, optionally phenyl-substituted aryl; pyridyl; ÜMenyl; furyl; Furylvinyl; Phenylvinyl, optionally phenyl-substituted phenylvinyl,

2 1

R represents mercapto, when R is a C 1 -C 6 -alkylamino-arylamino, arylamino which is optionally monosubstituted or polysubstituted at the phenyl nucleus,

2 1

R represents methylthio, when R is a C.sub.2 -C.sub.-alkylamino, optionally aryl group substituted by halogen at the phenyl nucleus, or

2 R for phenylcarbonylmethylenethio, if necessary substituted on the phenyl nucleus by halogen, if R is an arylamino group, optionally an unsubstituted or polysubstituted aryl group on the phenyl nucleus, '

1 2 R / R for C 1 -C 4 -alkylamino; Cyclohexylamine-; benzylamino; Arylamino, optionally on the phenyl nucleus or one or more times halogen-substituted aryl group, is,

prepared by reacting substituted aroyl or Hetaroyldmiden of the general formula II, in which R has the same meaning as in formula I, with substituted isothiocyanates to form compounds of formula III or with carbodiimides to form compounds of formula IV, in which R has the same meaning as in formula I and X is a hydrogen, a methyl group, C.-Cj.-alkyl group, phenylcarbonylmethylene group monosubstituted or polysubstituted by halogen on the phenyl nucleus and Y is a C 1 -C 4 -alkyl group; by hydrogen or halogen mono- or polysubstituted aryl group; Cyclohexyl and β-benzyl group, in an inert solvent in the presence of a base, e.g. Sodium hydride, at -20 ° C to + 10 ° C.

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The method according to the invention is illustrated by equation 1.

By the method according to the invention, for example, the compounds of Table 1, page 6 can be produced.

Example of Execution Example 1

N-Pyridoyl- (2) -N'-phenyl-S-methylisothiourea 6.1 g (0.05 mol) of 2-pyridoylamide are initially charged in 50 ml of absolute dimethylformamide (or dimethyl sulfoxide) and, with water cooling and nitrogen, with 1.5 g of sodium hydride added. Without further cooling, 6.75 g (0.05 mol) Phenylisothioqyanat are added dropwise and stirred for 4 hrs. At room temperature. Subsequently, 7.6 g (0.05 mol) of methyl iodide _/ dissolved in 20 ml of dimethylformamide with gentle cooling added dropwise. The solution is poured after 2 hours on ice, the solid product is filtered off with suction and recrystallized from ethanol / activated carbon.

Example 2

N- (3-bromobenzoyl) -N'-phenyl-S- (4-bromophenacyl) isothiourea 10 g (0.05 mol) of 3-bromobenamido are dissolved in 50 ml of absolute dimethylformamide under nitrogen at -20 ° C. with 1, Without further cooling, 6.75 g (0.05 mol) of phenyl isothiocyanate are added dropwise so that the internal temperature does not rise above 20 ° C. After 2 hours of stirring, 13.3 g (0.05 mol) of 4-bromophenacyl bromide dissolved in 30 ml of dimethylformamide is added dropwise, after stirring for 1 hour, the mixture is poured onto 250 ml of ice-water, and the resulting precipitate is filtered off with suction and recrystallized.

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Example 3

K-3-Puryl- (2) -acryloyl-N ^? - (i) -propylthiourea 6 »85 g (0.05 mol) of 3- (2-urothyl) acrylamide are added in portions in 50 ml of absolute dimethylformamide at 0 to -10 C under nitrogen with 1.2 g of sodium hydride. Subsequently, 6s75 g (0.05 mol) of Hienylisothiocyanat are slowly added dropwise and after stirring for 3 hours, the reaction mixture is poured into 200 ml of ice water. The resulting oil is extracted with ether or chloroform, the organic phase separated, dried, concentrated on a rotary evaporator and allowed to crystallize. From ethanol is recrystallized.

Example 4

N- (2-chlorobenzoyl) -N ', N "-dicyclohexylguanidine 2.13 g (0.02 mol) of 2-chlorobenzamide are dissolved in 40 ml of absolute tetrahydrofuran or dimethylformamide under nitrogen with 5 g (0.02 mol) of dicyclohexylcarbodiimide After stirring for 5 hours, it is poured into 300 ml of ice-water acidified with HCl, and the resulting precipitate is filtered off with suction and recrystallized.

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Table 1

R ¹ R ² ~ πΡ π J · \ j CcHcNH 6 5 SH KJ 1-C ₃ H ₇ -NH SH 90-93 CgH ₅ -NH SH 135 CgH ₅ -CH ₂ -NH SCH ₃ 144-46 CgH ₅ -CH ₂ -NH SCH ₃ 92-93 2-01-C ₆ H ₄ CgH-CH ₂ -NH SCH ₃ 160-62 4-CH ₃ OC ₆ H ₄ CgH ₅ -NH SCH ₃ 88-89 4-MO ₂ -C ₆ H ₄ CgH ₅ -NH SCH ₃ 148-50 CgH ₅ -NH SCH ₃ 103-05 0 CgH ₅ -NH SCH ₃ 96-99 CgH ₅ -CH = CH 3,4-Cl-CgH ₃ -NH SCH ₃ 158-60 CgH ₅ -CH = CH CgH ₅ -NH SCH ₃ 120-24 4-NO ₂ -CgH-CH = CH CgH ₅ -NH S-CH ₂ -CO-CgH 232-37 3-Br-CgH _{4 4} -Br (4) 142-45

3-Br-CgH ₄ CgH ₅ -NH S-CH ₂ -CO-CgH ₄ -NO ₂ (2) 123-24

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R ¹ R

3-Br-C ₆ H ₄ C ₆ H ₅ -NH S-CHg-C ₆ H ₄ Br (2) 93-94 4-NO ₂ -C ₆ H ₄ C ₆ H ₅ -NH S-CHg-CO-C ₆ H ₄ Cl (4) 122-29 C ₆ H ₅ -NH C ₆ H ₅ -NH 210 L ₀ JlCH-CH O-H.-NH b 11 C ₆ H ₁₁ -NH 103-05 ^ CH = CH C ₆ H ₅ -NH Γ- CrH, - NH b 5 106-07 2-Cl-C ₆ H ₄ C ₆ H ₅ -CH ₂ -NH C ₆ H ₅ -CH ₂ -NH 166-69 2-Cl-C ₆ H ₄ (DC ₃ H ₇ -NH (DC ₃ H ₇ -NH 120-24 2-Cl-C ₆ H ₄ C ₆ H ₁₁ NH C ₆ H ₁₁ -NH 172-73 c ₆ % (DC ₃ H ₇ -NH (DC ₃ H ₇ -NH 137-39 ^C 6 ^H 5 CgH ₅ -NH CGIL NH 90-91 4-CH ₀ OC ^ H. 3 ο 4 C ₆ H-CHg-NH C ₆ H ₅ -Chg-NH 16Ο-63 4-CH ₃ OC ₆ H ₄ OH _1-1 -NH b 11 C ₆ H ₁₁ -NH .170-74 6 5 C ₆ H ₅ -NH C ₆ H ₅ -NH 51-53 C ₆ H ₅ -CH = CH C ₆ H ₁₁ -H C ₆ H ₁₁ -NH 210-15

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G e g g Λ :

^ C

Y-N = C = N-Y

H ⁺

R-C-N = Cll O

nc

NHY ^ NHY R-C-N = C

U ^ NHY

Claims (1)

- £ - 233863 7 Erfindungganspruch A process for the preparation of novel N-aroyl and Hetaroylimiden of the general formula I, in which R is an aryl, optionally 'at the Rienylkern one or more times halogen-substituted aryl group; Phenylvinyl; Furylvinyl-5-furyl-pyridyl or thienyl group, where R / R is a mercapto ; methylthio; C.-C.sub.t-alkylamino; Arylamino, optionally substituted on the phenyl nucleus or polysubstituted aryl group; Benzylamino- or cyclohexylamino group, characterized in that substituted aroyl or HetaroyMmide the general ibrmel II in which R has the same meaning as in formula I, with substituted isothiocyanates to compounds of formula III or with substituted carbodiimides to compounds of the formula IV, in which R has the same meaning as in formula I and X is a hydrogen; a methyl-C ₁ -C ₅ alkyl; phenylcarbonylmethylene group substituted one or more times by halogen on the phenyl nucleus and Y is a C ₁ -C 6 alkyl; by hydrogen or halogen mono- or polysubstituted aryl; Cyclohexyl and benzyl group, are reacted in an inert solvent in the presence of a base such as sodium hydride at -20 ° C to + 10 ° C. To do this, 1 page formulas and % page table