DE1618146A1 - Process for the production of Dithionaxalsäurediamiden - Google Patents

Description

BADISOHB AUILIH- & SODA-J ¹ ABBIK AG 1 Rl SI / R

F Ίζ Ί '<? -ΐΥέ. ~? Our signs; OZ 24 852 WB / Bb

Ludwigshafen am Rhein, April 27, 1967

• Process for the production of dithionoxalic acid diamides

This invention relates to a process for the preparation of Dithionoxalsäurediamiden by conversion of halogenethanes, ethenes or ethines with sulfur and ammonia or amines.

The production of dithionoxalic acid diamide, which is attached to the nitrogen atoms is unsubstituted by reacting with dicyan Hydrogen sulfide has long been known (Annalen der Physik und Chemie, Volume 24, page 167; MeMgS Anna 1 en der Chemie, Volume 38, - Page 514} Reports of the German Chemical Society, Volume 22 (1889), page 2655; Journal of Practical Chemistry, Volume 29, (1884), page 129). Substituted diamides can by reaction aforementioned diamides are produced with appropriate amines. Dithionoxalic acid diimides' can only be obtained laboriously and in unsatisfactory yield. Also a method described in U.S. Patent 2,551,283, the vinyl ether or vinyl ester reacts with sulfur and amines to give dithionoxalaic diamides, satisfactory in yield and uniformity the Endatoffe does not.

It has only now been found that dithionoxalaic diamides are advantageous iriilltp when you use haloethanes, -ethenes or ethines

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Converts sulfur and ammonia, primary or secondary amines, sulfur and ammonia or amine each being approximately stoichiometric Amount, based on the halogen compound, or used in excess.

The implementation can be done in the case of the use of mono, Tetra-, hexachloroethane, vinylidene chloride or dichloroacetylene and cyclohexylamine are represented by the following formulas:

CHGl ₂ -CHCl ₂ + 2S + ^)

SS

ClCSCCl + 2S + 4 / ~ VnH ₂ - > (3 ~ ^ΝΗ - ° - °

SS

H ₂ C = GCl ₂ + 3S + 4 / "" N-NH ₂ > \ _J- NH-CC-NH- / ~~ \ +

+ H ₂ S

01, C-CCl, + 4S + -

■> ■> \ f c. \ r " "

S S

+ 2 SCl ₂

CH ₅ -CH ₂ Cl + 5S + 3 ^ ~ Λ-ΝΗ ₂ - > ^ y-NH-CC-NH- \ ~ 7 + \ _J NH ₅ Eq

SS

SS

+ 3H ₂ S.

In comparison to the aforementioned processes, the process delivers after of the invention, starting from easily accessible starting materials, a large number of dithionoxalic acid amides in a simple way

good yield and purity.

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A ^ isjgangesrto.ffe are ethane, Athene or! Thine, the one or more eli etarolx, 'preferably by bromine, iodine and / or ine "be ae ^ rid ere; @hli? R, s ^ s ^ ituiedrt sini _r used *

For example, there can be found ßaIo; geÄVerMHiu! Jge; Et sls raw materials,

Herd: AtiiyltKPoifiid "1 * a ^ Bteiil ^ ät ^ n ^ 1,1,1, -Trioiiloi— Oilor-t- ^ feroniatiian, 1,1 ^ tg ^ e ^ r & eltäoxiärtümxii Pentatrom- ,: tiiiyljodid, VinylidenljiOiiiid, cis ^ tmd t ^ a ^ e ^ s-Iiiölilor-

Cftloraeetyleii * ti

As a further starting material, Soliviefel comes into the reaction. For the formation of the dithione group, about 2 gram atoms of solsulfur are necessary for each halogen compound. One can use the sulfur a1? E: rötteii in Ijberseliuss. Amounts of about 3 to 5 Grammatoiii Sehwefel are zweekmäßig depending on the constitution of the Halagenverbindung to free "nascent hydrogen""or breakaway: to bine halogen ^a m the optimum amount of sulfur depends on the amount of the binding hydrogen or halogen from? as the above formulas illustrate. '

Likewise, primary or secondary amines are used in the reaction. About 2 moles of these basic starting materials are used per mole of halogen compound to form the two dithione oxalic acid amide groups. Ammonia or amines can, however, also be used in excess. Amounts of about 3 to 6 moles of basischexi starting materials reach appropriate depending on the constitution of the Halögenverbindung for use, vm the released Halogenwaaserstoffsäure.zu bind. Instead of the amounts of ammonia or amines _t used to bind the acid,

1OS813 / 1840 ^ '

can also use equivalent amounts of other acid-binding agents be fed to the reaction. AIa such are e.g. tertiary Amines, inorganic bases, such as alkali or alkaline earth oxides, hydroxides, amides, alcoholates or salts of polybasic acids.

Preferred basic starting materials are those in general formula

NH

R ₁ and Η «can be the same or different and each denotes hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical, in particular each with up to 20 carbon atoms, R ₁ and Rp also together with the nitrogen atom are a heterocyclic, in particular know 5- to 6-membered ring, it being possible for a carbon atom in this ring to be replaced by an oxygen or another nitrogen atom.

For example, the following bases can be used as basic starting materials be: ammonia, diethyl, ethyl, dibutyl, dodecyl, ethylmethyl, cyclohexyl, cyclooctyl, benzyl, hexylmethylamine, Aniline, naphthylamine, piperidine, morpholine, pyrrolidine, piperazine.

The reaction is generally carried out at a temperature between 80 and 200 ^° C., preferably between 80 and 150 ^° C., without pressure or under pressure, continuously or discontinuously, through

Original. INSPECTED

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161614

guided. If necessary, one uses under the reaction conditions inert organic solvents such as aromatic hydrocarbons, e.g. benzene, toluene, xylene; Alcohols, e.g. methyl, Butyl alcohol, cyclohexanol; Ethers, e.g. dibutyl ether, dioxane.

The reaction can be carried out as follows: A mixture the starting materials, possibly together with solvents and / or acid-binding agents, wildly for some time under good Mixing kept at the aforementioned temperature. Fun the mixture is cooled and filtered. The filter residue will washed free of chlorine ions with water and recrystallized from a suitable solvent, e.g. n-butanol. Stepped out of the FiI can by concentrating, the solution, filtration and appropriate work-up of the separated solid further fractions to be obtained in the end product. You can also use the filtrate concentrate completely and from the residue in the usual way, e.g. by distillation to isolate the end product.

The compounds which can be prepared by the process of the invention are valuable starting materials for dyes and herbicides.

The parts listed in the following examples mean parts by weight «

example 1

495 parts of cyclohexylamine and 64 parts of sulfur are heated ^{to 70 ° C. in 800 parts of toluene.} 131 parts of trichlorethylene are added gradually to the mixture at this temperature.

ORDINAL INSPECTED 10 9.8.1.3/1 «AO

- 6 - O.Z. 24

The mixture is then stirred for 10 hours at reflux temperature (110 ⁰ C). After cooling the mixture to 5 ⁰ O is filtered off from the precipitated precipitate and concentrated the. FiItrat. The filter residue is washed free of chlorine ions with water and recrystallized together with the residue from the toluene filtrate using n-butanol. This gives 182 parts Ν, Ν'-Dicyclohexyldithiooxalamid rom mp. 152 ⁰ C (corresponding to 64 # of theory, based on trichlorethylene).

Example 2

396 parts of cyclohexylamine and 64 parts of sulfur in 500 parts of toluene are heated to 80 ⁰ C. 100 parts of 1,2-dichloroethane are gradually added to the mixture over the course of one hour. The reaction mixture is kept for a further 24 hours under reflux at about 115 ⁰ C. A similar workup as described in Example 1, gives 112 parts of N, N'-Dicyclohexyldithiooxamid mp. 152 ⁰ C (equivalent to 40% of theory, based on the dichloroethane).

Example 3

297 parts of cyclohexylamine, 128 parts of sulfur and 63 parts of vinyl chloride in 300 parts of benzene are heated ^{to 1.20 ° C. in a shaking autoclave for 5 hours.} After cooling and releasing the pressure in the autoclave, the reaction mixture is freed from benzene , washed with water and recrystallized from ethyl alcohol. After separating off the excess sulfur, 187 parts of N ₁ N'-dioyolohexyldithiooxamide with a pp. 151 ⁰ O (corresponds to 66 # of theory) are obtained. qW6W * W- IN

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Example 4

594 parts of cyclohexylamine, Section 6 parts of sulfur and 166 parts of tetrachlorethylene are heated in 800 parts Toluene 30 hours TOO to 110 ⁰ C. After the mixture has cooled to about 5 ^° C., the precipitated solid is filtered off with suction. The filter residue is washed free of chlorine ions with water and dried. The toluene solution is also washed with water, dried and concentrated to 1/3. The crystals formed in this way are filtered off with suction and recrystallized from n-butanol together with the 1st filter residue. 179 parts of “N, N'-dicyclohexyldithiooxamide with a melting point of 152 ^° C. (corresponds to 64% of theory, based on the tetrachlorethylene used) are obtained.

■ - "■ .. Example 5

450 parts of beta-methoxyethylamine and 96 parts of sulfur are heated in 800 parts of ethyl alcohol at 60 to 7O ⁰ C and the mixture at die'ser temperature 166 parts of tetrachlorethylene gradually added. The reaction mixture is cooled another 25 hours at reflux temperature stirred at 5 to 1O ⁰ C. The precipitate formed is filtered off with suction, washed with water and recrystallized from ethyl alcohol. There are obtained 121 parts of N, if 'diss-methoxy-äthyldithiooxamid mp. 90 C ^0. The combined alcohol filtrates are concentrated completely, and 500 parts of water are added. A further 36 parts of Ν, Ιί'-di-ß-methoxyethyl-dithiooxamide are isolated from the water-insoluble residue. The total amount of end product corresponds to 67 % of theory, based on the tetrachlorethylene used »

. .- ■. ORIGINAL INSPECTED

"." ■ -. = "■ - ■■■ 1 0 93 12/18 40 · '■ -8-

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Example 6

535 parts of benzylamine and 64 parts of sulfur are ^{heated to 70 °} C. in 400 parts of ethyl alcohol and 131 parts of trichlorethylene are gradually added over the course of one hour. The reaction mixture is ^{heated to 85 °} C. for a further 20 hours, cooled strongly and filtered. The filter residue is washed free of chlorine ions with water, dried and recrystallized from n-butanol. There are 124 parts N, N ^! -Dibenzyldithiooxamide with a melting point of 115 ° C. The filtrate is concentrated completely, taken up in benzene, washed with water and dried. A further 37 parts of N, N'-dibenzyldithiooxamide can be obtained from the benzene solution by precipitation with ligroin. The total yield corresponds to # 54 of theory, based on the trichlorethylene used.

Example 7

295 parts propylamine, 64 parts of sulfur and 400 parts of ethyl alcohol are heated to .70 ⁰ C and 131 parts of trichlorethylene added gradually. The reaction mixture is stirred for a further 20 hours at 80 to 85 ^° C., cooled vigorously, and the precipitated hydrochloride is filtered off with suction. The filtrate is completely freed from ethanol, taken up in benzene, washed free of chlorine ions with water, dried and distilled. In Kp, 130 to 135 ⁰ C 127 parts are obtained N, N'-dipropyl-dithiooxamide (equivalent to 62 io of theory, based on trichlorethylene).

. -9-10 90 U / 1 840 ORIGINAL MSPECTCD

-9- --- O. * .. 24852. _lb1ÖU6

Example 8

A mixture of 396 parts of cyclohexylamine, 128 parts of sulfur and 99 parts. 1.1 ~ 600 parts of ethyl alcohol in dichloroethane is heated a total of 40 hours at 80 ⁰ C. After about 3 hours, vigorous evolution of hydrogen sulfide begins. When the evolution of hydrogen sulfide has ended (40 hours), it is ^{cooled to about 5 °} C. and the precipitated solid is filtered off with suction. The pilter residue is suspended in 300 parts of water, filtered and washed free of chloride ions with water. After recrystallization from acetone, 156 parts of NjN'-dicyclohexyldithiooxalamide are obtained. The ethanol filtrate is concentrated completely and the residue is recrystallized from acetone with the addition of a little activated charcoal. 52 parts of NjN '.- dicyclohexyldithiooxalamide are obtained. Total obtained 208 parts of N, ¥ ^r -Dicyclohexyldithiooxalamid from Pp. 152 ⁰ C (equivalent to 73 ^ of theory).

IMSPiCTED

109813- / 1840 '"-: - -10-

Claims (1)

- 10 - O ..- Z. 24 852 Claim. Process for the preparation of dithionoxalic acid diamides, characterized in that halogenethanes, -ethene or -ethines are reacted with sulfur and ammonia, primary or secondary amines, sulfur and ammonia or amine each in an approximately stoichiometric amount, based on the halogen compound, or in excess shot can be used. BADISCHE ANILIIi- & SODA-FABRIK AG Unt.'i. - - ■. 109813/1840