DE2211478A1 - Process and apparatus for the preparation of N-trihaloalkylthio compounds - Google Patents

Description

Patent attorneys

Dlpl.-Ing. R. BEETZ sen. _OO11 . *. _O

Dlpl-Ing. K. LAMPS3ECHT / C Λ I ** / O

Dr.-Ing. Fi. £ 3 ll E t Z Jr.
β M ü η ch θ η 22, Stoinsdorfetr. 40

233-18.454P (18.455H) 9, 3rd 1972

SPOLANA, närodni podnik, Neratovice (CSSR)

Method and device for the division of N-Irihalogen-

alkylthio compounds

The invention relates to a process for the preparation of N-irihaloalkylthio compounds by reaction of perchloromethyl mercaptan with the alkali salt of a corresponding organic nitrogen-containing compound, in particular a linide, in an alkaline-aqueous medium as well to a device for carrying out the method.

N-Trihalogenalkylthioverbindungen, in particular N-trichloromethylthiophthalimide and I-trichloromethylthiotetrahydrophthalimide are often in modern agrochemicals as effective i ^l ungizide used.

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These connections "are generally implemented by implementing ■ Perchloromethyl mercaptan produced with the alkali salts of the corresponding nitrogen-containing compounds. ! Differentiate The previously customary procedures for bringing about this implementation with each other only through the used reaction rate Basically, the conversion. tion of perchloromethyl mercaptan and alkali salt of the nitrogen-containing compound either in an inert kediuin of organic Solvents carried out, the reaction taking place slowly and the reaction mixture are heated must or it takes place .in an alkaline-aqueous medium, where the reaction takes place very quickly with strong heat dissipation goes. '

When carrying out the reaction in an inert medium the N-CDrichlornethylth'ioverbindungen is for example thereby obtained that perchloromethyl mercaptan to a suspension of the alkali salt of an imide in benzene or dioxane (US-PS 2,553,771 and GB-PS 716 553 and 666 636) or in isopropanol (US-PS 2,553,770 and 2,573,771) or in chloroform in the presence of tertiary Bases (US Pat. No. 2,856,410 and GB-Pb 787 168) are added or metered in.

By most processes for the preparation of N-'frihaloalkylthio compounds In an alkaline-aqueous medium, for example, the iviatrium imida becomes an aqueous solution Perchloromethyl mercaptan was added with vigorous stirring (US Pat. No. 2,553,775). This process not only runs Main reaction takes place at a considerable rate, but also the side reactions, i.e. mainly hydrolysis both reacting substances, with considerable heat emission, so that energetic cooling must be carried out.

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The disadvantage of all the processes described is the ^{low purity of the products, which is below 90 c} / o , and their unpleasant odor. Attempts have been made to eliminate these disadvantages through some improvements, such as, for example, according to US Pat. No. 2,713,058, German Pat of sodium imide or, according to US Pat. No. 2,553,776, by adding sodium or potassium chloride to the sodium imide solution or by mixing the perchloromethyl mercaptan with an emulsifier. Each process in which the perchloromethyl mercaptan is mixed with the ImId in the presence of an emulsifier while cooling with ice results in a product of about 88% purity. OSR-PS 107 115 therefore proposes a cleaning process according to which the product is dried and then suspended in 2% sodium hydroxide solution. This increases the purity to 90 ψ> , but the yields are very low and are around 60 <p of theory.

These disadvantages are intended to be eliminated by the invention will.

133 it was found that the poor quality of the product and the need for cleaning can surprisingly be eliminated by crushing the raw microcrystalline product immediately after its formation and bringing it into intimate contact with the reaction substance, whereby a Occlusion of perchloromethyl mercaptan in the drusen that forms can be prevented. In this, low odor scLlecnten "Jeise a product of great purity u ^v iJ of a created".

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The method according to the invention is accordingly characterized in that that the reaction with simultaneous crushing. or / and grinding the resulting from primary contact of the alkali salt the nitrogen-containing organic compound with perchlorine methyl mercaptan produced microcrystalline drusen will. V

A particularly suitable device for carrying out the method according to the invention comprises a cycle of! a mixing reactor, a disintegrator, a pump and a cooler. As a "disintegrator, for example, a plate passing" \

f homogeniser, a turbo mixer, a coloid or a pearl \

or ball mill, etc. can be used. ^

The process according to the invention can be carried out continuously or batchwise. In the event that the procedure is carried out continuously, the device according to the invention must be equipped with a metering device be. .

Examples example 1

360 liters of water, 11.2 kg of sodium hydroxide and 0.5 kg of Slovesol EL (Czechoslovakian trademark for an expoxidized fatty amine product) were placed in a mixing reactor. After cooling to ⁰ ° G, 41 kg of phthalimide were dissolved in this mixture, which was associated with a release of heat. After cooling down again to ⁰ ° G, 32 liters (51 kg) of perchloromethyl mercaptan were added with vigorous stirring. The reaction

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mixture was during the. The reaction was passed through a pass-through homogenizer, from where it was returned to the reactor via a *** cooler. During the reaction, the temperature and pH value were checked (the pH value should not drop below 8). After the reaction had ended, the suspended N-trichloromethylthiophthalimide was centrifuged off, washed three times with 300 liters of water and dried. 64.9 kg of N-triohlomethylthiophthalimide of 95.3 following purity were obtained. The yield was 75 $ "(based on the charged phthalimide) and 72.1 fä (based on d.as used _{Perohlormethylmercaptan);} '

Example 2

400 liters of water and .12.5 kg of sodium hydroxide were placed in a mixing reactor. After cooling, to -1 ⁰ 49 G "7 kg Tetrahydraphthalimid were dissolved in this solution. Then 32 liters of perchloromethyl mercaptan were made up and the reaction mixture was circulated through a Durobl homogenizer and a cooler. After the reaction had ended, the pH was adjusted to 9.5 and the product was centrifuged off, washed with 1200 liters of water and dried. Bs, 72 kg of N-Trichlormethylthiötetrahydrophthalimid 96.8 ^ purity obtained, (relative to the phthalimide · employed tetrahydro-) a yield of 84 "5 ° ß> (based on the charged Perohlormethylmercaptan) and 83.8 ° / o of .

Example 3 "-. · ■■

In a device consisting of a mixing reactor with a continuous homogenizer and cooler connected to it in the circuit

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a solution of 21.7 kg of phthalimide sodium salt in 270 kg of 7.4 'sodium hydroxide solution per hour and 27.1 kg of perchloromethyl mercaptan per hour were introduced. A continuously operating 'beitende filter and wash were 32.8 kg N-trichloro- ^"; won methylthiophthalimid per hour.

Example 4

In one of a mixing reactor, a continuous homogeneous! - eator, a cooler, a centrifuge and connecting circulation pipes existing device with feed pump. were continuously per hour. a solution of 21 kg of sodium tetrahydrophthalimide in 240 kg of 7% sodium hydroxide solution and 27.1 kg Perchloromethyl mercaptan initiated. From a continuously working filter and washing system were continuously 36 kg of If-Iriohlormethylthiotetrahydrophthalimid subtracted per hour.

Example 5

In Pig. 1 is one of several possible devices shown for performing the method according to the invention. The device according to the invention consists of a reactor 1, the one with a filling funnel 2, a stirrer (with iiiotqr 18), a measuring sensor 19 and a cooling jacket 17 with supply line 8 and discharge line 9 is equipped for the cooling medium, a continuous homogenizer 3, a circulation pump 4, a cooling. ler 5> a circulation pipe 10 and two dynamic filters 6 and 7. The filter system is provided with a discharge line 12 of the filter cake, with a reaction mixture feed line 11, with a water feed line 15, with two mother liquor outlets 13 and 14 and equipped with a product discharge 16.

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The gate direction according to the invention operates according to the following scheme: The reaction mixture is fed from the reactor 1 via the disintegrator 3 and the circulation pump 4 through the circulation pipeline 10 into the cooler 5. The biggest part
the reaction mixture is returned from the cooler to the reactor. The remainder of the reaction mixture is removed through the pipeline 11 and fed into the separation systems 6 and 7.
The product is removed from the separation system (dynamic filter system, continuous centrifuge, etc.).

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Claims (1)

221H7.8 Pat ent requests Process for the production of N-Trihalogenslkylthioverbindungen by reaction of Perchlormethnyluercaptan with the alkali metal. ^ An organic nitrogen-containing compound ü a ι urchgeke η η ζ calibrated η et, that the reaction with simultaneous crushing or / and grinding of the through primary contact desaliialisalzes nitrogen-containing organic compound with perchloromethyl mercaptan resulting aikroKristallinen jJrusen is carried out. 2. Process according to claim 1, characterized in that part of the ¹ reaction mixture is continuously discharged from the Icoüktionasystera and the product is isolated therefrom. 3. Device for performing the method according to the claims 1 and 2 with a reaction zone, a cooling circuit and / or a post-reaction zone characterized in that that in the circuit immediately behind the reaction zone (1) and / or in the reaction zone a disintegration zone (3) is switched on. 4. Apparatus according to claim 3, characterized in that the lieaktions- and / or post-reaction zone dan out a Trennζcue connects. 209842/1202 BATH ORIGINAL