CS197196B1 - Method of producing ammonium salt of ethylene-bis-dithiocarbamic acid - Google Patents
Method of producing ammonium salt of ethylene-bis-dithiocarbamic acid Download PDFInfo
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- CS197196B1 CS197196B1 CS676978A CS676978A CS197196B1 CS 197196 B1 CS197196 B1 CS 197196B1 CS 676978 A CS676978 A CS 676978A CS 676978 A CS676978 A CS 676978A CS 197196 B1 CS197196 B1 CS 197196B1
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- Prior art keywords
- ammonium salt
- etu
- ethylene
- bis
- ethylenediamine
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- AWYFNIZYMPNGAI-UHFFFAOYSA-N ethylenebis(dithiocarbamic acid) Chemical compound SC(=S)NCCNC(S)=S AWYFNIZYMPNGAI-UHFFFAOYSA-N 0.000 title claims description 13
- 150000003863 ammonium salts Chemical class 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 20
- FROZIYRKKUFAOC-UHFFFAOYSA-N amobam Chemical compound N.N.SC(=S)NCCNC(S)=S FROZIYRKKUFAOC-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000417 fungicide Substances 0.000 description 5
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 4
- 239000012990 dithiocarbamate Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000005802 Mancozeb Substances 0.000 description 2
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000011717 all-trans-retinol Substances 0.000 description 1
- 235000019169 all-trans-retinol Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000010171 animal model Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- YKSNLCVSTHTHJA-UHFFFAOYSA-L maneb Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S YKSNLCVSTHTHJA-UHFFFAOYSA-L 0.000 description 1
- 229920000940 maneb Polymers 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- -1 styrene diamine Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
predmetom vynálezu je sposob výroby amónnej soli kyseliny etylénbisditiokarbamidovej reakciou etyléndiaminu so sirouhlikom v prostredi amoniaku.It is an object of the present invention to provide an ammonium salt of ethylenebisdithiocarbamic acid by reacting ethylenediamine with carbon disulfide in ammonia.
Amonná soťkyseliny etylénbisditiokarbamidovej je doležitou východiskovou surovinou pre výrobu ditiokarbanátových fungicidov /pripravky na báze zinebu, manebu, mankozebu a 3aůšie/z ktoré patria v súčasnosti k základným pripravkom na chemickú ochranu polnohospodárskych kultůr proti chorobám sposobovaným roznymi druhmi húb.The ethylenebisdithiocarbamic acid ammonium salt is an essential starting material for the production of dithiocarbanate fungicides / preparations based on zineb, maneb, mancozeb and 3a / which are currently essential preparations for the chemical protection of agricultural crops against diseases caused by various species.
Z literatúry sú známe viaceré sposoby pripravy amónnej soli kyseliny etylénbisditiokarbamidovej /USA pat. č. 2 844 623, USA pat.č.2 855 418, DOS č.1 081 446, Chim.prom 3,Several methods for preparing the ammonium salt of ethylenebisdithiocarbamic acid / US Pat. no. 2,844,623, U.S. Pat. No. 2, 855,418, DOS No. 1 081,446, Chim.prom 3,
174-5, /1972/ a óalšie/.174-5, (1972) and beyond.
je tiež známez že jedným z nežiadúcich vedlajšich produktov, připadne produktov rozkladu samotných ditiokarbamátových fungicidov, pritomnom vo variabilnom množstve vo finálnych pr.ipravkoch, je etyléntiomočovina /ETU/· Doterajšie výsledky toxdkologického štúdia poukazujú na to, že ETU mSže maťtumorogenické, teratogenické a goiterogenické účinky na pokusné zvieratá. zvyšky ETU, stanovené na rázných kultúrach po ošetřeni diti okarbamidovými fungicidmi, naznačujú možné riziká aj pre zdřavie človeka, v pripade použivania pripravkov s vysokým obsahom ETU /Ethy lenethiourea, pure a Appl. Chem., vol. 49, pp. 675-689 /1977//.It is also known that one of the undesirable by-products. For products of decomposition themselves dithiocarbamate fungicides, present in variable amounts in the final pr.ipravkoch is ethylenethiourea / ETU / · The results so far toxdkologického study suggest that the order can ETU maťtumorogenické, teratogenic and goiterogenické effects on experimental animals. ETU residues determined on vigorous cultures after treatment with childhood carbides fungicides indicate possible risks for human health as well, when using high ETU / Ethylenenethourea, pure and Appl. Chem., Vol. 49, s. 675-689 (1977).
Teraz sa zistilo, že prvotným zdrojom tvorby ETU v ditiokarbamátových pripravkoch sú vodné roztoky příslušných soli etylénbisditiokarbamidovej kyseliny. Tak například pri re197 196 produkcii ktoréhokolvek zo známých spósobov pripravy amónnej soli etylénbisditi okarbamidověj kyseliny vzniká rózne množstvo ETU« Určujúce faktory vzniku ETU sú teplota a poradie pridávania jednotlivých reakčných komponentov.It has now been found that the primary sources of formation of ETU in dithiocarbamate formulations are aqueous solutions of the corresponding salts of ethylenebisdithiocarbamic acid. Thus, for example, in the production of any of the known methods of preparing the ammonium salt of ethylenebisdithiocarbamic acid, a varying amount of ETU is formed. The determinants of ETU formation are the temperature and the order of addition of the individual reaction components.
(alej sa zistila nová skutečnosti že pri zahrievani vodných roztokov amónnej soli ety lénbisditiokarbamidověj kyseliny na teploty vyššie ako 40 °C, prebieha rozklad uvedenej soli za súčasného vzniku ETU· Množstvo ETU je úměrné vzrastu teploty. Tak například pri zahrievani 28,3 g 38,3%-ného vodného roztoku amónnej soli etylénbisditiokarbamidovej kyseliny 50 hodin na teplotu 60 °C, vznikne 0,8 g 97,9%-nej ETU, čo představuje 85,7%-ný výťažok ETU vzhtadom na zníženie obsahu amónnej soli etylénbisditiokarbamldovej kyseliny, zahrievanim 27,8 g 38,3X-ného vodného roztoku uvedenej soli 0,5 hodiny na teplotu refluxu /cca 95 až 97 °C/ vznikne 1,9 g 95,2%-nej ETU, čo představuje 91,3X-ný výtažok tvorby ETU, vzhladom na zníženie obsahu amónnej soli etylénbisditiokarbamidověj kyseliny.(further, it was discovered that when aqueous solutions of ethylenebisdithiocarbamic acid ammonium salt were heated to temperatures above 40 ° C, decomposition of said salt took place, resulting in ETU formation. · The amount of ETU was proportional to the temperature increase. A 3% aqueous solution of ethylene-bis-dithiocarbamic acid ammonium salt at 60 ° C for 50 hours, yields 0.8 g of 97.9% ETU, which represents an 85.7% yield of ETU by reducing the ethylene-bis-dithiocarbamic acid ammonium salt content, heating 27.8 g of a 38.3% aqueous solution of said salt for 0.5 hour at reflux temperature (about 95-97 ° C) gave 1.9 g of 95.2% ETU, which was a 91.3% yield. formation of ETU, due to the reduction of the ammonium salt content of ethylenebisdithiocarbamic acid.
pre správný priebeh tvorby amónnej soli etylénbisditiokarbamidovej kyseliny s minimál nymi vedlejšími reakciami je doležité tiež poradie pridávania jednotlivých reakčných komponentov. je výhodné přidávat sirouhllk k miešanému roztoku zmesi etyléndlamínu a amoniaku, avšak toto platí tiež len pre určité teplotné rozmedzie. Například přidáváním sirouhlika k vodnému roztoku etyléndiaminu a čpavku pri teplote 45 °C vzniká až do 10 X tuhých nerozpustných vedtajšich látok, z ktorých sa identifikovalo ETU v množstve 20 X, elementárna sira 15 X, a zvyšok představovali produkty polysUlfidického charakteru.the order of addition of the individual reaction components is also important for the correct formation of the ammonium salt of ethylenebisdithiocarbamic acid with minimal side reactions. it is preferable to add carbon disulphide to the stirred solution of a mixture of ethylene amine and ammonia, but this also applies only to a certain temperature range. For example, adding carbon disulfide to an aqueous solution of ethylenediamine and ammonia at a temperature of 45 ° C produces up to 10% solid insoluble by-products, from which an ETU of 20%, an elemental sulfur of 15% was identified, and the remainder being polysulfide products.
Nedostatky známých spósobov výroby amónnej soli kyseliny etylénbisditiokarbamldovej reakciou etyléndiaminu so sirouhlikom v prostředí vodného roztoku amoniaku do značnej miery odstraňuje spdsob podlá vynálezu.The drawbacks of the known methods for producing the ammonium salt of ethylenebisdithiocarbamic acid by reacting ethylenediamine with carbon disulfide in an aqueous ammonia solution largely overcome the method of the invention.
podstata vynálezu spočívá v tom, že k zmesi styléndiaminu a amoniaku vo vzájomnom molárnom pomere 1:2 až 1:2,1, reagujúcej vo formě vodného roztoku, obsahujůceho 5 až 125 molov vody na 1 mól produktu reakcie, sa pri teplote 25 až 40 °C za stálého miešania přidá va sirouhllk v molárnom pomere 2:1 až 2,5:1 k východiskovému etyléndiaminu.The object of the invention is to react to a mixture of styrene diamine and ammonia in a molar ratio of 1: 2 to 1: 2.1, reacting in the form of an aqueous solution containing 5 to 125 moles of water per mole of reaction product, at 25 to 40 ° C. ° C, with stirring, is added in carbon disulfide at a molar ratio of 2: 1 to 2.5: 1 to the starting ethylenediamine.
Z takto získávaného vodného roztoku amónnej soli etylénbisditiokarbamldovej kyseliny možno vyrábat*kvalitné ditiokarbamátové fungicidy, ktoré obsahujú nežiadúcu ETU v množstvác odpovedajúcich len zlomkom percenta. o tom, že spósob pripravy amónrrej soli kyseliny etylénbisditiokarbamldovej má na obsah ETU pritomnej vo finálnych prípravkov niektorých ditiokarbamátových fungicidov doležitý vplyv, svedči skutočnosti že vzorky mankozebu /koordinačn komplex etylénbisd1ti okarbamidověj kyseliny s Mn a zn/, připravené z amónnej soli etylénbi.sdi ti okarbami dověj kyseliny, ktorej příprava prebiehala pri teplote 47 až 48 °C, obsahovali až 0,85 X ETU vzhtadom na zistený ebsah úěinnej látky, zati.alčo pri vzorkách mankózebu připravovaných rovnakým postupom z amónnej soli etylénbisditiokarbamidovej kyseliny pripravenej spósobom podlá vynálezu, obsah ETU nepřevýšil hranicu 0,1 X.High-quality dithiocarbamate fungicides can be produced from the aqueous ammonium salt of ethylene-bis-dithiocarbamic acid thus obtained which contain undesirable ETU in amounts corresponding to only a fraction of a percentage. that the process for the preparation of the ammonium salt of ethylenebisdithiocarbamic acid has an important influence on the ETU content present in the final formulations of certain dithiocarbamate fungicides, is evidenced by the fact that the mancozeb / co-ordinating complex of the ethylenebisdithiocarbamic acid with Mn and nb of the novel acid, which was prepared at a temperature of 47-48 ° C, contained up to 0.85 X ETU, based on the detected content of the active substance, whereas the ETU content did not exceed the ETU content of the mancoseb samples prepared in the same manner from the ethylenebisdithiocarbamic acid ammonium salt. 0.1 X.
Predmet vynálezu bližšie osvetlujú následujúce příklady.The following examples illustrate the invention in more detail.
přikladlEXAMPLE
Do troj hrdlej banky na 2 l, opatrenej míešadlom, teplomerom, prikvapkávacim lievíkom a odvzdušnenim prechádzajúcim cez spatný chladič sa vlialo 721 g vody a postupné sa priclalo 188,7 g 88%-ného vodného roztoku etyléndiaminu a 354,7 g 26,52-ného vodného roztoku amoniaku. Teplota obsahu banky sa upravila na 30 °c a pri tejto teplote sa za dobrého miašenia počas 1,5 hodiny po kvapkách přidalo pod hladinu 425 g sirouhlika. Obsah banky sa ešte 2 hodiny pri uvedenej teplote miešat, potom schladil na teplotu 16 až 17 °C a zvážil. Získalo sa 1 680 g čirého, žitého roztoku amónnej soli etylénbisditiokarbamidověj kyseliny, ktorý obsahoval 39,35 X žiadanej soli. výtažok představuje 97,1 % teorie.721 g of water was poured into a three-necked 2 L flask equipped with a stirrer, a thermometer, a dropping vial and a vent through a bad condenser, and 188.7 g of a 88% aqueous ethylenediamine solution and 354.7 g of 26.52- aqueous ammonia solution. The temperature of the contents of the flask was adjusted to 30 ° C, and 425 g of carbon disulfide were added dropwise to the temperature dropwise over 1.5 hours with good mixing. The contents of the flask were stirred for 2 hours at this temperature, then cooled to 16-17 ° C and weighed. 1680 g of a clear, lived ammonium salt of ethylenebisdithiocarbamic acid containing 39.35% of the desired salt were obtained. the yield was 97.1% of theory.
přiklad 2example 2
0o nerezového kotlá na 300 l, opatřeného vyhrievacim pláštom, teplomerom, turbinovým rýchlomiešadlom, privodnou rúrkou pre sirouhlik siahajúcou pod miešadlo a odvzdušnenim prechádzajúcim cez spatný, solankou chladený chladič, sa navážilo 86,5 kg vody, ku ktorej sa postupné přidalo 22,8 kg 87,3%-ného vodného roztoku etyléndiaminu a 45,5 kg 24,8%-ného vodného amoniaku. K vodnému roztoku týchto aminov sa v priebehu 1,5 hodiny pri teplote 30 až 35 °C přidalo 5.1 kg sirouhlika prívodom pod miešadlo. obsah kotlá sa ešte 2 hodiny pri tejto teplote miešal, potom vyhrial na 40 °C a hned'schladil na 17 °c. získalo sa 205 kg čirého 39,6%-ného vodného roztoku amónnej soli etylénbisditi okarbamidověj kyseliny, čo představuje 99,3%-ný výtažok teorie.86.5 kg of water was weighed into a 300 l stainless steel boiler equipped with a heating mantle, a thermometer, a turbine speed stirrer, an inlet pipe for carbon disulfide extending below the stirrer and a vent passing through a poor, brine-cooled cooler, to which 22.8 kg was gradually added. 87.3% aqueous ethylenediamine solution and 45.5 kg of 24.8% aqueous ammonia. To the aqueous solution of these amines, 5.1 kg of carbon disulfide was added over 1.5 hours at 30-35 ° C by feeding under a stirrer. the contents were stirred for 2 hours at this temperature, then heated to 40 ° C and immediately cooled to 17 ° C. 205 kg of a clear 39.6% aqueous ammonium salt of ethylenebisdithiocarbamic acid ammonium salt were obtained, which represents a 99.3% yield of theory.
Claims (1)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS676978A CS197196B1 (en) | 1978-10-18 | 1978-10-18 | Method of producing ammonium salt of ethylene-bis-dithiocarbamic acid |
| SU797770782A SU956470A1 (en) | 1978-10-18 | 1979-08-29 | Process for producing ammonium ethylbisdithiocarbanate |
| BG7944831A BG29477A1 (en) | 1978-10-18 | 1979-09-11 | Method for amonium salt of the ettelenebisdithiocarbamate obtaining |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS676978A CS197196B1 (en) | 1978-10-18 | 1978-10-18 | Method of producing ammonium salt of ethylene-bis-dithiocarbamic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS197196B1 true CS197196B1 (en) | 1980-04-30 |
Family
ID=5415460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS676978A CS197196B1 (en) | 1978-10-18 | 1978-10-18 | Method of producing ammonium salt of ethylene-bis-dithiocarbamic acid |
Country Status (3)
| Country | Link |
|---|---|
| BG (1) | BG29477A1 (en) |
| CS (1) | CS197196B1 (en) |
| SU (1) | SU956470A1 (en) |
-
1978
- 1978-10-18 CS CS676978A patent/CS197196B1/en unknown
-
1979
- 1979-08-29 SU SU797770782A patent/SU956470A1/en active
- 1979-09-11 BG BG7944831A patent/BG29477A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| SU956470A1 (en) | 1982-09-07 |
| BG29477A1 (en) | 1980-12-12 |
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