EP4121412A1 - Procédé de préparation de dthea hci - Google Patents

Procédé de préparation de dthea hci

Info

Publication number
EP4121412A1
EP4121412A1 EP20932102.5A EP20932102A EP4121412A1 EP 4121412 A1 EP4121412 A1 EP 4121412A1 EP 20932102 A EP20932102 A EP 20932102A EP 4121412 A1 EP4121412 A1 EP 4121412A1
Authority
EP
European Patent Office
Prior art keywords
hcl
water
dtea
reaction
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20932102.5A
Other languages
German (de)
English (en)
Other versions
EP4121412A4 (fr
Inventor
Anthony P. Haag
Pulikkottil Jacob THOMAS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AMSA Inc
Original Assignee
AMSA Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by AMSA Inc filed Critical AMSA Inc
Publication of EP4121412A1 publication Critical patent/EP4121412A1/fr
Publication of EP4121412A4 publication Critical patent/EP4121412A4/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/26—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/25—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated

Definitions

  • This invention generally concerns an improved process for preparing DTE A HCl from 1- decene and cysteamine HCl (CA HCl).
  • Solids may cause major difficulties with clogging filters and/or nozzles in applications requiring the formulation be pumped or sprayed.
  • the ability to remain as a pumpable, homogeneous material that is free of solids is essential to avoid costly and inconvenient heating and agitation operations during formulation operations and use.
  • W02001/041570 (Beilfuss) describes use of the same suite of additives as those in US 2008/0076803 above but they are used to improve the stability and lessen inhomogeneity of a different mixture of AIs.
  • US Pub Appln 2013/0217579 (W acker) describes a new low temperature solvent for pesticide formulations and includes addition of GLTS propylene glycol (PG) and glycerol to said formulations.
  • PG propylene glycol
  • Some of the disadvantages of using the Mariam reaction to produce DTEA HCl are: (1) achieving high conversion of reactants is difficult and requires multiple additions of catalyst and extended reaction times to achieve high conversion of reactants to DTEA HCl; and (2) dilution with the preferred solvent (water) produces a formulation with serious solidification/solids formation problems at low temperatures (defined as about 32°F to about 60°F).
  • BTS solvents mentioned are butyl alcohol, cyclohexanol, hexyl alcohol, isobutyl alcohol, ethylene glycol phenyl ether (a synonym for 2-phenoxyethanol (PE)) and propylene glycol phenyl ether (a synonym for l-phenoxy-2-propanol (PP)) and mixtures thereof.
  • PE 2-phenoxyethanol
  • PP propylene glycol phenyl ether
  • Some of the disadvantages of using Brady’s BTS with the products of these processes are: 1) addition of the BTS to the organic solvent-based reaction mixture results in higher overall product costs; and 2) adding additional organic chemicals to the formulation is problematic in the application of this product in industrial water treatment: organic solvents in the formulation are nutrients for microbial growth and make its control more challenging and costlier.
  • the amount of organic solvent in the formulation should be minimized to the extent possible.
  • a major limitation to extrapolation of Brady to other solutions is that the screening for low temperature stabilization was done, specifically, on a solution of DTEA HCl consisting of (approximately) 45 wt% DTEA, 45 wt% PG, 7 wt% water, and 3 wt% impurities.
  • PG is not LTS for this formulation, PG is a better solvent for DTEA HCl than water. Brady’s findings do not correlate well to other DTEA HCl formulations that do not contain PG.
  • the two methods for industrial-scale production result in formation of a solid product or a phase- separated mixture at above room temperature (i.e ., about 70 °F) as a reaction concentrate unless the reaction concentrate is sufficiently diluted with water or other diluents.
  • the EtOx process involves a reaction of decenethiol with ethyl-2-oxazoline without solvent at about 140 °C to form an intermediate that is immediately, in situ , hydrolyzed with additional heat and cone. HCl to form DTEA HCl. This material is directly pumped into another, larger reaction vessel (to avoid solidification of the product in the reactor as it is cools and of sufficient size for product dilution).
  • the second vessel contains water and PG to form a reaction concentrate medium similar to that obtained from the Mariam MEAH process.
  • the MEAH process involves a reaction of cysteamine HCl with decene in propylene glycol which then diluted with water or a water-PG mixture which is then further diluted with water (Mariam, U.S.Pat. 5087757A, Eur. Pat. Appl. (1989), EP 320783 A2 19890621).
  • the reaction concentrate from the EtOx is diluted before drumming and has a typical content of about 18 wt% DTEA HCl, 16 wt % PG, and 66 wt % water after dilution.
  • the MEAH process reaction concentrate can be made readily at 45-50 wt% DTEA HCl or, as described in Mariam (Example 1), as a 15 wt% DTEA HCl solution in PG and water (-15 wt% DTEA HCl, -16 wt % PG, and -67 % water). Brady notes that a typical Mariam reaction concentrate consists of 45 wt% DTEA, 45 wt% PG, 7 wt% water, and 3 wt% impurities.
  • the undiluted reaction concentrate from the Marriam reaction process must drummed while the reaction mixture is still hot because the mixture solidifies at around 60 oo F and can form solids in the solution even around typical room temperature.
  • Commercial formulations typically contain from about 5 to about 15 wt% DTEA HCl prepared by dilution of the reaction concentrate with the appropriate amount of water. From solubility data (see Figures land 2), -15 wt% DTEA HCl a PG/water mixture provides a solid-free solution of DTEA HCl at room temperature, and this serves as a basis for the wt % DTEA HCl, PG and water in reaction mixture (Mariam, Example 1).
  • the solubility of DTEA HCl in the ME AH reaction concentrate medium (Mariam, Example 1) and of the EtOx process reaction medium (Relenyi, Example 1) when each is diluted with water is about 15 wt% at about 68 °F, about 10 wt % at about 63 °F, and about 5 wt% at 55 °F.
  • the drummed Mariam reaction concentrate is rock solid at typical room temperatures and must be heated to form a liquid in order to get it out of the drum for further dilution or other formulation uses.
  • the present invention describes an improvement over known processes for the production of 2-(n-dccylthio)cthylaminc HCl (DTEA HCl) in which the reaction efficiency is improved and incorporates an Additive that is both a low temperature stabilizer (LTS) and a reaction Co- solvent to provide a commercial formulation with improved low temperature stability with minimal post reaction processing.
  • DTEA HCl 2-(n-dccylthio)cthylaminc HCl
  • LTS low temperature stabilizer
  • reaction Co- solvent a reaction Co- solvent
  • the present invention concerns a process for preparing 2-(n- decylthio)ethylamine HCl (DTEA HCl) comprising reacting decene and cysteamine HCl, with (a) a catalyst, (b) water, and (c) an Additive of the Formula (A):
  • Ph is phenyl; n is 0 or 1 ; k is 2-4; and m is 1-3; that provides the 2-(n-dccylthio)cthylaminc HCl as a concentrated mixture in about >90% yield, wherein such concentrated reaction mixture is further diluted with water to provide a low temperature stable (LTS) liquid product.
  • LTS low temperature stable
  • Additional Additive can be added directly to the concentrated reaction mixture or as part of the dilution with water or after the dilution with water.
  • the amount of Additive present after dilution with water in the final solution is from about 1 to about 30 wt% or from about 2 to about 20 wt%.
  • the amount of Additive used in the reaction is from about 10 to about 49 wt%.
  • the low temperature stability of the resulting product means at temperatures from about 32°F to about 60°F.
  • a stable liquid product means that the product has no solids formation or separation of any phases at the low temperatures.
  • the amount of product present in the final solution is from about 2 to about 25 wt%; or from about 5 to 15 wt%.
  • the reaction is run under an inert atmosphere, at a temperature from about 70°C to about
  • the yield of the DTE A HCl product from the present reaction is >90%, often >95%, even when run on a commercial scale and can be further optimized.
  • Figure 1 graphically represents the water solubility of DTE A HCl in an unprocessed Mariam reaction mixture ( i.e ., approximately 47-51% DTEA HCl, 18-21% PG, 21-27% water). There is no LTS used so the data is comparative.
  • Figure 2 graphically represents the solubility of pure DTEA HCl when the only solvent is water. This shows the solubility of pure solid DTEA HCl in water with no LTS used. The data is comparative.
  • Additive means a compound that is both a Co-solvent (defined below) and LTS (defined below)
  • AI active ingredient azo catalyst means, preferably, one of the following:
  • BA means benzyl alcohol, as depicted by the following structure
  • BTS means an GLTS subset as defined by Brady and applicable only to temperature stability of a specific formulation of DTEA HCl
  • CA means cysteamine or 2-aminoethanethiol or 2-mecaptoethylamine
  • Co-solvent means a solvent used with water in the reaction of this invention
  • Decene means 1-decene, C 10 H 20
  • DiEPh means diethyleneglycol phenylether or 2-(2-phenoxyethoxy)ethanol, as depicted by the following structure
  • DTEA means H -dec y lthioethy la m i nc or 1- decylthioethylamine or 2-(l- decylthio)ethylamine g means grams
  • GLTS means generally well known, widely used low temperature stabilizers without defining the stabilization or temperature range of use but for specific applications h means hour or hours HCl means a hydrochloride salt L means liter
  • LTS means a compound that acts as a low temperature stabilizer, in which a liquid solution remains homogeneous and does not become solid, or contain solids (precipitates), or undergo phase separation at low temperature (low temperature means from about 32°F to about 60°F) and low temperature stability is determined by instrument measurement or visually by the absence of solid particulates (crystalline or other solid forms) or by absence of any solidification of the liquid.
  • min means minute or minutes
  • m L means milliliter
  • PA 2-phenylethanol as depicted by the following structure
  • PE 2-phenoxyethanol, as depicted by the following structure
  • PG means propylene glycol, as depicted by the following structure
  • PP means l-phenoxy-2-propanol, as depicted by the following structure
  • RT room temperature or ambient temperature, from about 20°C to about 25 °C or about 72°L sec means second
  • Solids formation includes but is not limited to formation of a solid phase within the original liquid phase, which includes but is not limited to crystallization; if the amount of solid is substantial, the entire volume may appear solid Water means water purified by reverse osmosis (RO) as used in the present examples, but this is not critical wt% means percent by weight
  • low temperature stabilizers are thought of as an interchangeable, generic class such that one may simply choose any one of a myriad of known GLTS agents.
  • These GLTS agents are generally the last component of the formulation to be described and commonly include the phrase ‘as needed’ .
  • post- reaction GLTS selection provides no guidance for selection of a suitable reaction solvent, especially free radical reaction where solvent selection is especially critical to reaction success (see, for example, Litwinienko, G.; Beckwith, A. L. J.; Ingold, K. U. “The frequently overlooked importance of solvent in free radical syntheses” Chem. Soc. Rev. 2011, 40 (5), 2157-2163. DOI: 10.1039/C ICS 15007C).
  • a preferred form of DTEA HCl for sale is a liquid in various concentrations, for example about 5 to about 15 wt% DTEA HCl, whereas the DTEA HCl is produced most efficiently at a higher concentration in the reaction.
  • the reaction mixture must be diluted to yield the final formulation for sale.
  • Water is the preferred dilution solvent due to its low toxicity and low cost and environmental preference. Also, water is not a nutrient for microbial growth during product application, so lowering organic solvent content by increasing the water content provides benefit in applications.
  • the reactants for this present process are decene (which is soluble in several organic solvents and relatively insoluble in water), and CA HCl (which is soluble in aqueous systems).
  • the present process requires a water solvent with an organic co-solvent that serves multiple functions (including improving homogeneity of the reaction process and also providing FTS for the product formulation), and a catalyst. When these two reactants are mixed with the solvents and catalyst, the reaction occurs.
  • An Additive is needed as a Co- solvent to ensure effective contact and reaction of the reactants in the initial two-phase mixture in a high reaction yield, which also serves as FTS for the final product that is needed for handling and storage. Finding an Additive that will work as both a Co-solvent and FTS in this specific reaction has proven difficult.
  • DTEA HCl product from the reaction must remain as a homogenous liquid to provide accurate and simple transfer of the product without solidification, phase separation such as solids formation by crystallization (which is a problem in prior systems).
  • Aqueous solutions with minimal organic content are preferred in this process and its ultimate formulation as they are inexpensive, relatively non-hazardous, and especially, provide minimal organic nutrients for microbial growth in end use applications.
  • aqueous propylene glycol is the reaction solvent of choice.
  • PG propylene glycol
  • the product obtained from a PG-based process when diluted with water unfortunately forms solids at low temperatures (as defined above) and requires addition of FTS to achieve a homogeneous liquid at 32°F to 60°F.
  • BTS 2-phenoxyethanol
  • PP l-phenoxy-2-propanol
  • the present process uses an Additive that is both a Co-solvent and LTS. This has the advantages given below. Determining what Co-solvent that works well for the present reaction and is also LTS was neither appreciated nor attempted by the prior art.
  • GLTS such as propylene glycol (PP), glycerol, or ethylene glycol
  • PP propylene glycol
  • glycerol glycerol
  • ethylene glycol ethylene glycol
  • SA benzyl alcohol
  • PP l-phenoxy-2-propanol
  • the present Additives that are Co-solvents used in the present reaction and used as LTS, can be optionally further added to the aqueous DTEA HCl product solution to provide a stable liquid at temperatures down to at least 32°L.
  • a formulation that forms solids at low temperatures such as these which are commonly encountered in storage and use of this product is not practical and is problematic.
  • solids form in a formulation it is often difficult to regain homogeneity.
  • Storage in specially heated storage areas to prevent lower temperatures or using heat and agitation to melt and re-blend the mixture is time-consuming, expensive and inconvenient.
  • Heterogeneous mixtures are difficult to pump, can clog nozzles and filters, do not meter well, and cannot be used to provide consistent or accurate dosing.
  • Suitable Co-solvents of the present invention are phenyl containing alcohols, such as 2- phenoxyethanol (PE) and 2-phenylethanol (PA), preferably those having a significant water solubility of about 1 to about 10 wt%.
  • the amount of Additive (LTS/Co-solvent) used in the reaction is from about 10 to about 49 wt%, and preferably from about 15 to about 35 wt%.
  • the effective Additives are represented by the following Formula A:
  • Ph is phenyl
  • n is 0 or 1
  • k is 2-4
  • m is 1-3.
  • Additives of Formula A are PA, PE, and DiEPh.
  • Some examples of GLTS found ineffective as Co-solvents are BA, PP and PG. Thus, it is not apparent to one skilled in this art what will work as an Additive in the process based on prior known reactions.
  • the mixture When carrying out the current reaction, the mixture initially has two liquid phases; namely, an organic phase containing decene and an aqueous phase containing cysteamine HCl (CA HCl).
  • the latter aqueous phase also contains the catalyst.
  • decene must have sufficient solubility in or contact with the aqueous phase.
  • the present phenyl alcohol Co-solvents have a suitable balance of polar and nonpolar character which facilitates the required mixing and solubilization in the reaction. These Co-solvents also possess suitable properties to solubilize the final product at low temperatures from about 32°F to about 60°F to avoid solidification, solids formation and/or or phase separation as LTS agents.
  • These present LTS are present in the final product solution from about 1 to about 30 wt%, preferably from about 2 to about 20 wt%. Many of the prior used solvents do not have such properties and do not provide these desired results.
  • the present process requires that a free radical initiator is used.
  • a free radical initiator is used.
  • hydrogen peroxide and the azo initiator are taught by Mariam (discussed above).
  • Mariam the preferred azo initiators that Mariam taught were azoh/ ' .snitrilcs which are not water soluble.
  • Mariam also provided no data for the azo initiators, which have been found in this present testing that even water soluble azo initiators are not effective with PG as the solvent.
  • an azo catalyst with PE or PA solvent in the present reaction alone resulted in the desired LTS product.
  • the present preferred catalysts are azo catalysts that are water soluble such as:
  • This process provides a final product which is formed from the present reaction as a solution containing: a) from about 2 to 25 wt% of DTEA HCl, preferably from about 5 to about 15 wt%, b) additional water and Additive added after the reaction if needed in an amount from about 1 to about 30 wt% of Additive, preferably from about 2 to about 20 wt%.
  • the final product provides a low temperature stability of at least from 32°F to about 60°F.
  • the letter examples are comparative examples.
  • the numbered examples are directed to the compounds of the present invention.
  • Decene was purchased from Shell.
  • PE was obtained from Nexeo.
  • Benzyl alcohol and PA were purchased from Sigma- Aldrich.
  • PP was obtained from GNS Technologies LLC.
  • CA HCl was purchased from Hangzhou Qianjin Technology Ltd.
  • V-50 was purchased from Wako.
  • VA-044 was obtained from Sigma-Aldrich. H 2 O 2 was purchased from GFS Chemicals, Inc., as a 50% aqueous solution and then diluted to 1.5- 1.8% solution with water.
  • the general present reaction conditions are:
  • Temperatures from about 25°C to about 120°C (preferably from about 74°C to 77°C preferred);
  • Atmosphere is air, nitrogen or argon
  • Catalyst concentration from about 0.01 to about 5 wt%, preferably from about 0.1 to about 1 wt%;
  • Decene concentration from about 1 to about 40 wt%, preferably from about 15 to about 30 wt%;
  • Cysteamine HCl concentration from about 1 to about 40 wt%, preferably from about 15 to about 30 wt%;
  • Water concentration from about 10 to about 49 wt%, preferably from about 15 to about 35 wt%;
  • Additive concentration from about 10 to about 49 wt%, preferably from about 15 to about 35 wt%; and Optionally are: 36 wt% HCl added from about 0.01 to about 1 wt%; DTEA HCl added from about 1 to about 5 wt%, preferably from about 0.5 to about 2 wt%.
  • the mixture was stirred and heated to 65°C using a water bath. To this mixture 0.1 mL of concentrated HCl was added followed by 10 mL of decene. The addition of hydrogen peroxide solution was then started along with the remaining decene, maintaining the reaction temperature below 80°C (about 74°C to 77°C is preferred). Hydrogen peroxide solution was added over a period of 40 min. and decene was added over a period of 20 min. The reaction mixture was stirred for another h after completion of the addition of hydrogen peroxide while maintaining the reaction temperature below about 80°C (about 74°C to about 77°C temperature is preferred).
  • Addition of PE in the range of about 5 wt% to about 10 wt% to a 15 wt% DTEA solution produces homogeneous solutions at both RT and upon prolonged storage - several days- at 32°F.
  • the weight percent DTEA HCl in the solutions after addition of PE ranges from about 6.5 wt% to about 7 wt%.
  • PE in the range of about 13 wt% to about 16 wt% to a 15 wt% DTEA solution (prepared from commercial DTEA HCl concentrate by diluting with water) produces homogeneous solutions at both RT and upon prolonged storage - several days- at 32°F. Below approximately 13 wt% PE the solution is homogeneous at RT, but solid at 32°F.
  • the weight percent DTEA HCl in the solutions after addition of PE ranges from about 12.5 wt% to about 13 wt%.
  • a 16.7 wt% DTEA solution (prepared as described above for 7.5 and 15 wt% solutions) was diluted with either PE or PG to provide solutions that contain 13.9 wt% of DTEA HCl and 16.6 wt% of either PG or PE.
  • the solubility of pure DTEA HCl in water is 11 wt% at 67°F and less than 1 wt% at 56°F (see Figure 2).
  • PG is a better for solvent than water for DTEA HCl, but PG does not provide low-temperature stability (LTS) to the mixtures containing it.
  • Example 2 The general procedure outlined in Example 2 was followed using 72 g of decene, 62 g of CA HCl, 75 g of Co-solvent, 75 g of water, 2.75 g of DTEA HCl, 0.6 wt% of VA-044 in 10 mL of RO water. No solid DTEA HCl was added to this reaction. Analysis showed DTEA HCl was produced in 77.4% with 81% conversion in 2 h.
  • Part A Propylene glycol/Hydrogen peroxide process - dilution with water and 2-phenoxyethanol (PE)
  • DTEA HCl product mixture (200 g, 50 wt% DTEA HCl) was mixed at RT with 380 g of water and 86.6 g of 2-phenoxyethanol (PE) to obtain 666.6 g of 15% DTEA HCl as a clear solution containing 13% of 2-phenoxyethanol (PE). Further 1:1 dilution at RT with water provided a 7.5% DTEA HCl as a clear solution containing 6.5% of 2-phenoxyethanol (PE).
  • Part B 2-Phenoxyethanol/V-50 Process - dilution with water and 2-phenoxyethanol (PE)
  • DTEA HCl product mixture (270 g, 47.4 wt% DTEA HCl) was mixed at RT with 544 g of water and 39 g of 2-phenoxyethanol (PE) to obtain 853 g of 15% DTEA HCl as a clear solution containing 13% 2-phenoxyethanol (PE) (270 g of the product mixture had already 72 g of PE). Further 1 : 1 dilution at RT with water provided a 7.5% DTEA HCl as a clear solution containing 6.5% of 2-phenoxyethanol (PE).
  • Example 6 Crystallization behavior
  • Part B Reaction product from 2-phenoxyethanol/V-50 Process diluted with water and 2- phenoxyethanol (PE)
  • Part C Purified DTEA HCl diluted with water and 2-phenoxyethanol (PE) A first 15% DTEA HCl solution containing 13% 2-phenoxyethanol and a second 7.5% of
  • DTEA HCl containing 6.5% of 2-phenoxyethanol prepared from DTEA HCl were both homogeneous liquids at 32°F.
  • DTEA HCl is essentially insoluble in water at 32°F and a 15 wt% DTEA HCl solution in water forms solids well above RT. (See Figure 2).
  • DTEA HCl The product formed from the present process, is used in industrial water treatment systems for control of biofouling and corrosion.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé amélioré de préparation de DTEA HCl à partir de décène et de cystéamine HCl à l'aide d'un catalyseur, d'un solvant et d'un co-solvant pour aider la réaction et assurer une stabilisation à basse température de la solution de produit obtenue.
EP20932102.5A 2020-04-19 2020-04-19 Procédé de préparation de dthea hci Pending EP4121412A4 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2020/028897 WO2021216029A1 (fr) 2020-04-19 2020-04-19 Procédé de préparation de dthea hci

Publications (2)

Publication Number Publication Date
EP4121412A1 true EP4121412A1 (fr) 2023-01-25
EP4121412A4 EP4121412A4 (fr) 2024-01-31

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Country Status (6)

Country Link
EP (1) EP4121412A4 (fr)
KR (1) KR20230065194A (fr)
CN (1) CN115298166B (fr)
CA (1) CA3179998A1 (fr)
MX (1) MX2022012786A (fr)
WO (1) WO2021216029A1 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5087757A (en) * 1987-12-16 1992-02-11 The Dow Chemical Company Preparation of alkylthioethylamine salts
US5025038A (en) * 1989-03-03 1991-06-18 The Dow Chemical Company Process for the preparation of antimicrobial formulations of 2-(alkylthio)ethanamine hydrohalides
TW202429B (fr) * 1991-02-27 1993-03-21 Hoechst Ag
DE19951328C2 (de) * 1999-10-20 2002-03-14 Schuelke & Mayr Gmbh Kältestabile Konservierungsmittel
DE102006045065A1 (de) * 2006-09-21 2008-03-27 Schülke & Mayr GmbH Mikrobizide Zubereitung auf der Basis von 1,2-Benzisothiazolin-3-on

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CA3179998A1 (fr) 2021-10-28
KR20230065194A (ko) 2023-05-11
MX2022012786A (es) 2022-11-09
CN115298166A (zh) 2022-11-04
EP4121412A4 (fr) 2024-01-31
WO2021216029A1 (fr) 2021-10-28
CN115298166B (zh) 2024-05-31

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