DE1020633B - Process for the preparation of derivatives of 2,5-dimercapto-1,3-, 4-thiadiazole - Google Patents

Description

GERMAN

The invention relates to a process for the preparation of new derivatives of 2,5-dimercapto-1,3,4-thiadiazole.

The structure of these new compounds and their preparation from N-substituted thiocarbamyl halides and mercaptides of 1,3,4-thiadiazole-2,5-dithiol is expressed by the following equation:

N N S

il Il ^R 'x Il

M-S-C C-S-M +2 N-C -X

N N

, N-C-S-C

C-S-C-N

in which M is hydrogen, an alkali metal or ammonium, X is a halogen and R ₁ for itself is alkyl, aralkyl, aryl, alkaryl, cycloalkyl or alkyl-substituted cycloalkyl radicals, while R ₂ for itself is alkyl, aralkyl, Mean cycloalkyl or alkyl-substituted cycloalkyl _{radicals or R 1} and R ₂ together can also mean polymethylene radicals.

The above equation explains the formation of diesters of 1,3,4-thiadiazole-2,5-dithiol; in the same way but the corresponding monoesters are also available if the two starting materials are equimolar Quantities apply, instead of, as in the formation of the diesters, 2 moles of the N-substituted thiocarbamyl halide to 1 mole of dimercaptide. Sometimes such monoesters can be used as valuable by-products in the extraction process the diesters are obtained and are then isolated from the reaction mixture with advantage.

The monoesters are of course monomercaptides, and such monomercaptides can become monomercaptan monoesters be implemented by the action of suitable acids, e.g. B. hydrochloric or sulfuric acid. If so desired the monomercaptide monoesters can be further substituted with any of the N-substituted ones used here React thiocarbamyl halides, forming a diester.

The products according to the invention, including the diesters, the monomercaptide monoesters and the monomercaptan monoesters, can through the general formula

procedure

for the production of derivatives
of 2,5-dimercapto-1,3-, 4-thiadiazole

Applicant:

The Pennsylvania Salt Manufacturing
Company, Philadelphia, Pa. (V. St. A.)

Representative: Dr. W. Beil, lawyer,
Frankfurt / M.-Höchst, Antoniterstr. 36

2MX

N- - N

-C

C-S-C-N

are reproduced in which R ₁ and R _{2 are the} same BeRoland Henry Goshorn, Trenton, Mich.,
and William Walter Levis jun. "Wyandotte, Mich.
(V. St. A.),

have been named as inventors

have meanings as in the above equation and where Z is hydrogen, alkali metals, ammonium or the remainder

R ₁

R,

N —C -

means in which R ₁ and R _{2 have the} same meanings as above.

The diester products contain two N-substituted thiocarbamyl radicals, which can be the same or different from one another. It goes without saying that R ₁ and R ₂ , if they are each replaced individually, can be identical or different to one another in any of the N-substituted thiocarbamyl radicals which are doubly substituted on the nitrogen atom by monovalent radicals of the type mentioned above, and this applies to both for the products according to the invention as well as for the halide starting materials.

Examples of the alkali metals are sodium and

Potassium, examples of halogens chlorine, bromine and iodine.

The number of carbon atoms is preferably each

that of the nitrogen atom of the N-substituted thiocarbamyl halides attached hydrocarbon residues not more than 12, in particular not more than 8. Of particular Of interest are those compounds in which the carbamate nitrogen is replaced by 2-alkyl radicals with 1 to 8 carbon atoms is substituted per alkyl radical.

709 309/323

3 4

To carry out the reaction, the initial formation and the like are used; they impart such lubricants

substances brought together and in the presence of a Lö- also better properties for use under

solvent or liquid thinner at high pressure. In particular, they are also highly effective

sets, which is essentially one of the prevailing vulcanization accelerators for rubber; namely are

conditions is inert. Water is excellent for this purpose - in contrast to the US patents

extremely suitable. You can convert the mercaptide into the N-sub- 2 331749 and 2 766 223 described thiodiazole

enter substituted thiocarbamyl halide, or reassigned - not just activators for vulcanization

returns. In general, however, the N-substi- accelerator is used, but vulcanization

thiocarbamyl halide, which is in the form of an accelerator.

finely divided powder, a liquid, a solution io The dimercaptid starting materials can after

or suspension may be present in an aqueous solution method of U.S. Patent 2,685,587, the N-sub-

of the mercaptid. substituted thiocarbamyl halides e.g. B. after the

This aqueous solution of the mercaptide can be used in any of the procedures described in US Pat. No. 2,466,276 and

have any concentration, up to the Sätti- German patent 817 908,

limit at the respective temperature, and some substituted thiocarbamyl chlorides are often included

sometimes it may even be desirable to have some mer-free sulfur mixed in. From this sulfur

captid is present in solid form. If the chlorides are used, they can optionally be used before they are used

Sodium dimercaptides is e.g. As a 20 ° / ₀ solution as starting materials for the process of the present

very functional. Invention to be exempt. But you can also do that

The N-substituted thiocarbamyl halide can form sulfur-containing mixtures without separating the Schweder use aqueous solution or suspension of the mercaptide rock for the reactions, because the sulfur as a fine powder, but better in a liquid state, e.g. B. is inert to the reactants and the finished as a melt (in the case of usually solid halides), products. In this case the products contain or in the form of a solution. Of course, sulfur as an impurity that is required ■ in each case The solvent to be used is not critical, 25 can be removed later if necessary, provided that it is essentially inert among the The following examples are illustrative Conditions of reaction is. The other invention can also, but should not be objectionable in any way Quantity fluctuate within wide limits, although restrict.

it is often desirable to use as much solvent as the reported manufacturing procedures

that the halide is kept in the liquid phase. 30 of starting materials is used in the context of this invention

Suitable solvents are e.g. B. Hydrocarbons, protection not desired,

like hexane, petroleum naphtha, benzene, toluene etc., or example 1

chlorinated hydrocarbons such as carbon tetrachloride, _TT ",", ",. ,. , "_,.

or chlorobenzene ^Ά > production of lS ^ -Tniadiazole ^ .S-disodium-

The melting points of the N-substituted thiocarbamyl 35 mercaptide

halides, which according to the present invention as a 3-1 three-necked flask with stirrer, dropping funnel

Raw materials are used, reflux condenser and thermometer can be provided within wide limits, will fluctuate with; some of them are charged still case of temperature following starting materials: 117 g of a liquid temperatures, far below the g for the preferred 54.5 ° / ₀ aqueous hydrazine solution (2 mole of hydrazine), embodiment of the method in question 40160 ( 4 mol) sodium hydroxide in 750 g of water and lie. In this case, the 0.5 g of a wetting agent, namely p-tert.-octyl-phenoxy, which does not react in reaction, acts primarily as a diluent for the halide, if such a liquid is used, ethoxyethyl-dimethyl-benzylammonium chloride, in 30 g. Water.

possibly also as a solvent for the After stirring started, 40 g of sulfur

driving product. 45 carbon added. In the next 10 minutes

Regardless of the order of addition, the carbon disulfide went into solution, and the tempe raw materials and the particular physical temperature of the reaction mixture rose from 20 to 30 °. Form these substances before mixing together, it is the addition of carbon disulfide continued, very useful, the reaction mixture during the and the reaction temperature rose to 45 °, whereupon Implementation to stir. 5 ° it was held between 40 and 45 ", namely in the

The reaction already takes place at room temperature, initially through an ice bath and later through external, preferably at temperatures below 100 °, for example heating. A total of 304 g (4 moles) of sulfur between 0 and 100 °, between 20 and 80 "carbon within I ³ ',, hours added best However, it can also operate at lower temperatures, Stirring was continued for 30 minutes..;

however, the conversion rate is usually 55 at the same time the same temperature conditions were lower, and the liquid mixtures are more viscous. continued as above. In the first part of this time, higher temperatures can also be used, but there was a smell of hydrogen sulphide on the vent consider. ^6o This was quickly ^{heated to about 80:} and at this

The reaction pressure is arbitrary, that is, if the temperature is below or approximately maintained, it is approximately 1 hour over-atmospheric; normal pressure is also suitable. long stirred. All the while developing You can also periodically, semicontinuously or completely continuously, copious amounts of hydrogen sulfide; towards the end it was work. Development weaker.

The reaction products are easy to clean and ⁶ 5 The solution was then allowed to cool to about 40 ° within exactly the same as that of the next hour, according to the chemical analysis. As the possibility of desired and expected substances. These carbon disulfide losses by entrainment in the body are highly effective in increasing the stability of the hydrogen sulfide evolution, lubricants such as hydrocarbon lubricating oils were stirred for 1 hour and at the same time 61 g and fats, against oxidative decomposition, sludge 70 (0.8 mol ) Carbon disulfide added. It evolved

some hydrogen sulphide was left in the early stages of this stirring; but towards the end the development stopped practically on. Then the stirring was stopped and there was some unreacted carbon disulfide perceive in the reaction mixture. To eliminate this carbon disulfide, the Mixture therefore warmed to about 60 ° and the system was under reduced pressure for a few minutes Pressure set.

Di-n-butyl-thiocarbamyl chloride reacted using the same facility and general procedure as in Example 1 described, was used. The addition of the carbamyl chloride solution was completed after 30 minutes, during which time the temperature of the reaction mixture was kept between 35 and 40 °.

The stirring lasted 30 minutes. Then 340 g of an aqueous solution were added in which 1.5 moles of sodium sulfide were included, whereupon again 1 hour at

The solution was then cooled to approximately 25 ° and stirred at 30 °. It was then filtered, diluted with water with 650 g of water and washed to remove one and dried at 40 to 45 °. The small amount of brown tar obtained was filtered, leaving a clear
yellow filtrate was obtained. So you got a solution with

about 20 weight percent 1,3,4-thiadiazolyl-2,5-disodium mercaptide.

tene 1,3,4-thiadiazolyl-2,5-bis- (di-n-butyl-dithiocarbamate) was a light brown powder, m.p. 72.5 to 76.5 ^c ; the yield was 458 g = 93.3% of theory.

A sample of this 1,3,4-thiadiazolyl-2,5-bis- (di-n-butyl-dithiocarbamate) was recrystallized from acetonitrile; Mp 77.5 to 78 °.

Analysis for C ₂₀ H ₃₆ N ₄ S ₅

Calculated N 11.37%;

N found ll, 45 ° / _0, 11.56%.

Example 3

1 mole of S ^ thiadiazolyl ^ S-disodium mercaptide in 960 g aqueous solution, was in a glass vessel

b) Preparation of diethylthiocarbamyl chloride

In a 1-1 Erlenmeyer flask equipped with a stirrer,
Thermometer and gas inlet pipe was fitted,
was 592 g (2 moles) of molten anhydrous Tetra-20
given ethyl thiuram disulfide. This liquid became
vigorously stirred; then chlorine was passed in quickly,
while the temperature of the reaction mixture was kept between 65 and 70 °. Overall were
142 g (2MoI) of chlorine initiated within 30 minutes. 25 of 3.81 contents poured, the thermometer, elec- The resulting reaction mixture contained diethylene-heated dropping funnel and high-speed stirrer verthiocarbamyl chloride and sulfur. The chlorination was seen. Dimethylthiocarbamyl chloride (247 g = 2 moles) was interrupted and the mixture to about 105 ° ^C. was added to the funnel and warmed in the molten state and stirred until all the free sulfur state was maintained; this chloride had previously been distilled in the diethyl thiocarbamyl chloride had dissolved. This became 30 minutes and contained virtually no free sulfur, required about 30 minutes. The chloride became the mercaptide solution with stirring

given within 30 minutes, the temperature c) preparation of 1,3,4-thiadiazolyl-2,5-bis- _the mixture was kept at 30 to 40 °.

(diethyldithiocarbamate) _{To the} obtained thick sludge, 200 g

2 moles of 1,3,4-thiadiazolyl-2,5-dinatrium mercaptide were added to water, followed by 15 minutes and more as a 20% aqueous solution in a 7.71 capacity addition of 20 g of a 20% aqueous sodium vessel was stirred with a thermometer, electrically heated dropping hydroxide solution for a further 15 minutes, funnel and high-speed stirrer (7500 rpm). During the filtration, a solid material was obtained, that with water

After starting the stirrer, the top was washed and dried at 60 °. One received solution of diethylthiocarbamyl chloride 40 described so 275 g (= 85% of theory) of an ivory-colored with a temperature of about 100 ° in the dropping powder with melting point 181 to 185 ° (with decomposition), the

was relatively insoluble in common solvents such as methanol, acetone and benzene. However, it dissolved in hot dimethylformamide and could be recrystallized from this solvent. After suctioning off and washing with acetone and drying at 80 °, it showed a melting point of 193 to 194.5 ° decomposition) and the following analytical value: C ₈ H ₁₂ N ₄ S ₅

(under

₈₂

Calculated N 17.27%,

found N 17.33%, 17.38%.

Example 4
A 15% aqueous solution of 1,3,4-thiadiazolyl

funnel filled and slowly added to the mercaptide solution within 45 minutes, with occasional was cooled to keep the temperature between 25 and 35 °.

LTm the resulting thick sludge better flowable

To make it, water (500 g) was added. The mixture was then stirred for a further 45 minutes and at the same time 552 g a 28.2% aqueous solution of sodium sulfide (2 moles of sulfide) added to the mixture to remove the free Solubilize sulfur; then stirring was continued for 1 hour.

The mixture was then filtered, the solid residue

washed well with water and dried at 50 °.

The l, 3,4-thiadiazolyl-2,5-bis- (diethyl-di- 55 2,5-disodium mercaptide, which contains 1 mole of the mercaptide)

thiocarbamate) was a light brown powder with which was added to the apparatus of Example 1.

Mp. 93.5 to 95 ° and weighed 665 g = 85% of theory. After turning on the agitator, the top became one Sample l, 3,4-thiadiazolyl-2,5-bis- (diethyldithio- mentioned, diisobutyl-thio- decanted from the sulfur)

carbamate) was made once from methanol and once from carbamyl chloride with a temperature of approximately

Recrystallized acetonitrile; the pure product ^{obtained 6o} 50 ° placed in the dropping funnel and within

2 hours while maintaining a temperature of 35 to 40 ° in the reaction vessel in this. Then, an aqueous sodium sulfide solution weighing 326 g containing 1 mole of the sulfide was added to the The mixture was added, which was stirred for a further hour and then filtered. One remained on the filter white solid body consisting of 1,3,4-thiadiazolyl-2,5-bis- (diisobutyl-dithiocarbamate) existed and after drying at 50 ° melted at 106 to 109 °. His

melted at 95 to 96
Analysis for C ₁₂ H ₂₀ N ₁ S ₆
Calculated C 37.86%;
N 14.72%;

found C 38.00%, 37.85%;
N 14.65%, 14.73%;
Example 2
1 mole of 1,3,4-thiadiazolyl-1,2,5-disodium mercaptide

H 5.30%,

S 42.12%;

H 5.38%, 5.33%,

S 42.17%, 42.35%.

was as an aqueous solution (1348 g) with a sulfur-containing 70 amount was 463 g = 94% of theory. He was

Purified by recrystallization from acetonitrile, a white crystal powder with a melting point of 109.5 to 111 ° arose, the analysis of which was as follows:

and drying at 90 °, a pure product having a melting point of 185 ° to 186 ° (with decomposition) being obtained.

Analysis for C ₁₄ H ₂₀ T

N ₄ S ₅ :

Stirring was added to the solution over the course of 15 minutes, the reaction temperature being between 40 and 45 °. Then water (400 cc) was added to make the mixture more fluid and the stirring continued

U ₂₀ U ₃₆ JN ₄ S _{5 5 Calculated N} 13.85%;

Calculated N 11.37%, S 32.53%; found N 13.63%, 13.75%.

found N 11.37%, 11.51%, S 32.4%. _Beis . ^ _Η

Example 5 _{An aqueous} solution (150 g) of 1,3,4-thiadiazolyl-

1 mol of symm.-di-n-butyl-dicyclohexyl-thiuramide sulfide io 2,5-disodium mercaptide, which 0.15 mol of this mercaptide with the melting point 93 to 95 ^C was in Nn-butyl-N-cyclo-, was in brought a glass vessel of 1 l, the hexyl-thiocarbamyl chloride according to the general method with thermometer, electrically heated dropping funnel and proceeding in Example 1 implemented. High-speed stirrer was provided. After starting stirring

A 15% strength aqueous solution of 1,3,4-thia was then N-ethyl-N-phenylthiocarbamyl chloride (mp. 58 to diazolyl ^ .S-disodium mercaptide, the 1 mol of this mixture 15 59 °; 60 g = 0.3 mol) in the molten state with binding, in the device according to Example 1
given and stirred in it. Then that was mentioned
filtered chloride with only a small amount left in it
dissolved sulfur added within 30 minutes,

heating of the dropping funnel was not necessary. 20 continued for 1 hour. Meanwhile, the reaction mixture became between The solid product obtained by filtration became

45 and 50 ° held. The mixture obtained, washed with water, rinsed with 750 ecm of methanol as an oil product, was dried for 45 minutes and at 40 °. The 1,3,4-thiadilang thus obtained stirred, the oil slowly forming a solid mass of azolyl-2,5-bis- (N-ethyl-N-phenyldithiocarbamate) was a froze, which turned crystalline upon standing overnight. 25 ivory-colored powder weighing 58 g and with The solid constituents of the aqueous solution had a melting point of 165 ° to 171 °. It was recrystallized from toluene, which are then powdered, well siert with cold water and filtered by filtration, rinsing with methanol and Washed out and rinsed with 1500 ecm of methanol and dried at 40 ° pure recovered. The purified were. The remaining powder was bound with 1 1 acetone was a white crystal powder, melting point 179 to 180 °, Slurried, filtered, rinsed with 11% acetone and at 30 its analysis was as follows:

40 ° dried. 360 g of 1,3,4-thiadiazolyl- _{rw MQ were obtained in this way}

2,5-bis- (N-n-butyl-N-cyclohexyldithiocarbamate) as a brown powder that melted at 134 to 141 °.

This product was made by dissolving it in benzene

50 °, filtration, addition of an equal volume of hexane, cooling the solution to 10 °, filtration and rinsing cleaned with cold acetone; this recrystallization was followed by another from a mixture of equal parts of the volume

Ethyl acetate and acetonitrile. The cleaned up, on this

The compound thus obtained had to be kept liquid after drying 40.

at 40 ° a white powder with a melting point of 145 to 146 °. The establishment and general working method of the

Calculated N 11.76%,

S 33.63%;

found N 11.95%, 12.02%, S 33.6

Example 8

The dibenzyl-thiocarbamyl chloride used for this experiment was a waxy solid mass but easily in the dropping funnel by heating to 60 °

-24 "-40-" 4 "

Game 7 were also used here, around 0.3 mole of the above chloride with 0.15 mole of 1,3,4-thiadiazolyl-2,5-disodium mercaptide implement that in 150 g

Analysis for C

Calculated N 10.28%;

found N 10.20%, 10.17%. 45 aqueous solution were included. The attachment to

the chloride lasted at a temperature of the reaction

Example 6 mixed from 25 to 30 ° 15 minutes. Then it became

267 g of cyclopentamethylene thiocarbamyl chloride mixture were stirred for a further hour at about 40 °, with a 10% aqueous solution of 1,3,4-thiadi- A rubber-like plastic mass was formed and

azolyl-2,5-disodium mercaptide, in which 0.75 mol of mercaptide 5 ° is an aqueous solution; the latter was decanted that were contained, using the same make-up mass by quenching to -10 ° to solidify and the same general procedure as in the brought and then powdered. The powder was with Example 1 described, implemented. The deposition of the 500 ecm 5% sodium hydroxide solution takes 30 minutes Chloride to the mercaptide solution took place in 30 Mi- 0 °, stirred, filtered off, washed with ice water and utes (heating of the dropping funnel was unnecessary), stirred at 55 with 1 1 of methanol at 10 °, with it again a reaction temperature of the mixture of 45 to rubbery in nature. The methanol 50 °; the mixture was then decanted for a further 30 minutes, and the gummy mass in 250 ecm touched. Then 326 g of an aqueous solution was dissolved with hot acetone. The hot solution was filtered, containing 1 mole of sodium sulfide within one to remove a small insoluble residue, Added hour with stirring to the reaction mixture. 60 and the filtrate is mixed with methanol until it becomes cloudy, The resulting sludge was filtered, the solid was cooled to 10 ° and more methanol was added; the total amount of methanol added was 500 cc. The solid that crystallizes out of the solution Substance was filtered and air dried. 65 It weighed 25 g and melted at 132 to 139 degrees; she was that 1,3,4-thiadiazolyl-2,5-bis (dibenzyl-dithiocarbamate).

This compound was made by dissolving in hot acetone, adding twice the volume of methanol and cooling the solution recrystallized. According to Filtra-

Washed residue with water, then rinsed with 1 liter of methanol and dried at 90 °. 138 g of a powder with a melting point of 183 to 185 ° ^{C. remained} (with decomposition).

The solubility of this powder in the most common Solvents were not enough for recrystallization. However, this succeeded from a mixture of pyridine and dimethylformamide in proportion

1: 3 parts by volume, subsequent washing with acetone 70 tion and drying in the air left the compound

9 10

Preparation as an ivory-colored powder with a m.p. 139. Approximately 0.3 mol of dicyclohexyl-thiocarbamyl chloride

up to 141 ° and the following analysis: were dissolved in 100 ecm benzene. This solution was

C ₂ HN ₄ S ₅ : (without heating the dropping funnel) with stirring

Calculated N 8.91 ° /; quickly to 50 g of an aqueous solution of 1,3,4-thiadi-

Found N 8.57 ° / _0, 8.67%. ⁵ azolyl ^ .S-dinatrium mercaptide given, the 0.15 MolMer-

contained captid. During this addition, the Tem example 9 temperature of the reaction mixture between 35 and 40 °

The di-sec-butyl-thio used in this experiment is kept, as is stirring for a further 45 minutes, carbamyl chloride was found as a gelatinous red solid. The reaction product, a yellow gummy mass,

Get mass; of this, 73 g in 100 ecm acetone were separated from the liquid and carefully mixed with it for use in the Um- 11 described below, methanol leached, whereby the gum becomes a settlement solved. white crystal mass was converted. This was

It was again used as the means and general work successively with water, 2 ° / ₀ sodium hydroxide solution and according to Example 7; the chloride solution washed with water, rinsed with methanol and was (without heating, in the dropping funnel) dried within 15. The yield was 70 g, melting point 179 ° to 184 °. from 20 minutes with stirring to 150 g of an aqueous The compound was found to be quite insoluble in

Solution of 1,3,4-thiadiazolyl-2,5-disodium mercaptide of a number of solvents with which the surrounding, which contained 0.15 moles of the latter; tempecrystallization was attempted. That's why it got through The temperature of the reaction mixture was further purified between thorough leaching with acetone. To and held at 40 °. The stirring lasted for a further 1 hour, including filtering off the acetone and drying it at 45 ° under the same temperature conditions. and now had the mp. 186 to 188 °.

The mixture consisted of an oil and an aqueous analysis for C ₂₈ H ₄₄ N ₄ S ₅ :

Solution; it was poured into 1 liter of warm water, 10 Mi- Calculated N 9.39 ° /;

Nuts stirred with it and then cooled to 10 °. found N 9.06%, 9.06 ° /.

The oil solidified to a rubbery solid mass, the 25th

aqueous solution was decanted off. The solid mass example 12

was successively with 500 ecm 2 ° / ₀ iger sodium hy- 970 g of an aqueous solution of 1 mol of 1,3,4-thiadiazo-

droxydlösung, then at 2 ° / ₀ hydrochloric acid solution and lyl-2,5-dinatriummercaptid were placed in a 2-1 beaker

last washed with 11% warm water. poured that with thermometer, electrically heated

The solid material (red and rubbery) was fitted with a dropping funnel and high-speed stirrer. 204 g Dissolve in hot methanol, cool the solution, remove the distilled diethylcarbamyl chloride in the funnel separating the precipitated solid, which was kept in a molten state, was washed internally with cold methanol and drying halfway through 45 minutes with stirring to the mercaptide air cleaned. This product was added to 1,3,4-thiadiazolyl solution, the temperature of which was kept at 30 ° 2,5-bis- (di-sec-butyldithiocarbamate), was yellow and turned crimson.

stallin, it melted at 96 to 97 degrees. Then dilute sodium hydroxide solution was added; the

thereafter clearly alkaline mixture turned red. she

Analysis for C ₂₀ H ₃₆ N ₄ S ₅ : Was filtered off, leaving on the filter mainly

Calculated N 11.37%; the 1,3,4-thiadiazolyl-2,5-bis (diethyldithiocarbamate) as

found N 11.21%, 11.25%. 40 cakes remained. This was washed with water

and stirred with dilute sodium hydroxide solution. The resulting sludge was nitrided again; That was

repeated several times.

The di-n-octyl-thiocarb used in this experiment- The all alkaline filtrates were combined,

amyl chloride was a pale reddish liquid 4-5 then the solution was acidified with hydrochloric acid, wo-color. through the 1,3,4 ~ thiadiazylol-2-thiol-5-diethyl-dithiocarb-

It became the same. Device as in Example 7 with amat was precipitated in solid form. In this state, 125 g of an aqueous solution of 1,3,4-thiadiazolyl- it was red, but was charged by recrystallization from 2,5-disodium mercaptide, which contained 0.125 moles of methanol as a light yellow solid. With stirring, approximately 0.25 moles of the 5 <> were collected and dried. Its amount was the abovementioned chloride (without heating the drop, 20 g after purification, melting point 119.5 ° to 120.5 °; the funnel) was quickly added to the solution. The temperature analysis for C ₇ H ₁₁ N ₈ S _{5 was} :

the reaction mixture was between 35 and 45 °. Calculated N 15.9 ° /;

during the addition of the chloride and a further 1 ^x / ₂ hours found N 16.2%.

further stirring. 55

The reaction product, an oil, was sequentially Example 13

with water, methanol, 10% sodium hydroxide solution, the setup and general procedure according to

5% hydrochloric acid and water. Finally, Example 1 was used, in order to rinse 359 g (2 mol) of diisopropylene with methanol and dry thiocarbamyl chloride (melting point 69 ° to 71 °) at 1.0 mol under reduced pressure. There remained 20 g of 1,3,4-thiadiazolyl- ^6o !, S ^ -thiadiazolyl ^ S-disodium mercaptide to implement 2,5-bis- (di-n-octyldithiocarbamate), a liquid with which 960 g of its aqueous solution contained was. The following analysis: chloride was molten in the course of a

Added hour of the solution, the reaction mixture

C ₃₆ H ₀₈ ^ US ₅ : was kept between 50 and 60 °.

Calculated N 7.82%; ⁶ 5 After the addition of the chloride, another 30 minutes

found N 7.42%, 7.30%. stirred for a long time; then 82 g of an aqueous sodium

. -I ₁₁ sulfide solution added containing 0.25 mol of sulfide, and

eispie 11 ^ _as Q _61n Jg ₀ J ₁ - was stirred for a further hour. Of the

The same facilities were used, and the same resulting sludge was filtered and the sludge that was thereby agglomerated Procedure as used in example 7. 7 ° remaining solid residue washed with water, again

filtered and washed again with 11% cold methanol. After drying, 245 g of a solid residue remained, which melted at 111 to 114 °.

This substance was dissolved in 600 ecm of acetonitrile at 75 °, the solution obtained was used to remove a My amount of insolubles was filtered and the filtrate was cooled to 10 °. A crystal precipitate formed from the solution, which was recovered by filtration; it was then rinsed with 500 ecm cold methanol and dried at 50 °. The 1,3,4-thiadiazolyl -2,5 - bis - (diisopropyl - dithiocarbamate) obtained in this way weighed 147 g and consisted of pale yellow crystals with a melting point of 116 ° to 117.5 °.

The acetonitrile filtrate obtained above remained in an ice bath for 2 hours, whereby a crystalline Precipitation farewell. This was filtered, rinsed with cold methanol and dried at 50 °. The thus obtained 3,4-bis (diisopropylthiocarbamyl) -1,3,4-thiazolidine-2,5-dithione consisted of light greenish yellow crystals (30 g) and melted at 147 to 149 °.

The N and S determination of the compound melting at 116 to 117.5 ° gave the following analysis:

for N 12.76 and 12.71%;
for S 36.3%.

25th

In the connection from F. 147 to 149 ^{:: the} following values were found:

N 12.88, 12.81;
S 36.9%.

Theoretical values for both products would have been 12.83 for N and 36.70% for S. The two connections are therefore isomeric with each other.

The lower melting isomer is relatively insoluble in hot and cold benzene, while the higher melting point is soluble therein.

The lower melting point could become the higher melting point be isomerized by mixing 10 g of it (melting point 116 to 117.5 °) with 100 ecm of toluene for 12 hours boiled at reflux (vessel temperature about 110 °); the fixed connection went into solution soon after the toluene came to the boil. The solution then remained Mar even when it cooled to room temperature. With the addition of 400 ecm of hexane, however, a solid precipitate separated out if the mixture was left for 2 hours left at 10 °. This precipitate was removed by filtration and rinsed with 200 ecm of cold methanol and dried. This resulted in 6 g of an ivory-colored powder with a melting point of 144.5 to 147.5 \ This substance was dissolved in 20 ecm hot toluene, whereupon 100 ecm hexane was added again. At the Standing this mixture at 20 °, a solid precipitate crystallized out, which was collected on the filter with 50 ecm of methanol was rinsed and dried. It was ivory in color, weighed 4 g, and melted at 147.5 bis 149 °. A mixed melting point determination with the higher melting point compound, its analysis data have already been communicated, proved the identity of both substances.

Although the invention is explained by name with reference to the use of N-substituted thiocarbamyl chlorides has been, you can use the analogous N-substituted thiocarbamyl bromides and iodides in aqueous or

React non-aqueous solution with the mercaptides to form the desired compounds.

In the above description the invention has been illustrated using aqueous media, but it is not a necessary condition, but other suitable solvents or diluents can be used, especially if they practically do not take part in the reaction or are inert under the respective conditions, e.g. B. Hydrocarbons of an aliphatic or aromatic nature, such as benzene, toluene or hexane, or chlorinated aliphatic ones or aromatic hydrocarbons such as carbon tetrachloride or chlorobenzene.

Claims (1)

PATENT CLAIM: Process for the preparation of derivatives of 2,5-dimercapto-1,3,4-thiadiazole of the general formula N N Z - S - C C-S-C-N; characterized in that a compound is used in aqueous or non-aqueous solution or dilution the general formula N-- -N S-C C - S - Z in Z hydrogen, alkali metals, ammonium or radicals of the formula S N —C - denotes, where in the latter R ₁ alone denotes alkyl, aralkyl, aryl, alkaryl, cycloalkyl or alkyl-substituted cycloalkyl radicals and R ₂ alone denotes alkyl, aralkyl, cycloalkyl or alkyl-substituted cycloalkyl radicals, or R ₁ and R ₂ together can mean polymethylene radicals, at temperatures advantageously between 20 and 80 ° with a compound of the general formula R ₁ R, N - C - X in which X is halogen and R ₁ and R _{2 have the} same meaning as above, the two reactants being reacted in a molar ratio of 1: 1 or 1: 2. Considered publications: Swiss Patent Specifications No. 279 553, 281963; U.S. Patent No. 2,331,749. © 7C9 809/325 12.57