WO2017068348A1 - Forme cristalline ii de la tétraacétyléthylènediamine - Google Patents

Forme cristalline ii de la tétraacétyléthylènediamine Download PDF

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Publication number
WO2017068348A1
WO2017068348A1 PCT/GB2016/053270 GB2016053270W WO2017068348A1 WO 2017068348 A1 WO2017068348 A1 WO 2017068348A1 GB 2016053270 W GB2016053270 W GB 2016053270W WO 2017068348 A1 WO2017068348 A1 WO 2017068348A1
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Prior art keywords
tetraacetylethylenediamine
crystalline form
taed
solid composition
agent
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PCT/GB2016/053270
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English (en)
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Anant Raghunath PARADKAR
Sachin Abasaheb KORDE
Sudhir Kashinath PAGIRE
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University Of Bradford
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

Definitions

  • the present invention relates to a new crystalline form of tetraacetylethylenediamine (TAED) and a method for its preparation.
  • the present invention also relates to solid compositions comprising tetraacetylethylenediamine in this crystalline form, and in particular, to solid detergent or bleaching compositions.
  • Tetraacetylethylenediamine (CioHi6N 2 0 4 , IUPAC name: N,N ' -l,2-Ethanediylbis(N- acetylacetamide); CAS registry number: 10543-57-4) is a well-known bleach activator which is mainly used in solid detergents or additives for laundry washing and dishwashing.
  • Solid detergent compositions typically incorporate "active oxygen” bleaching agents, such as sodium perborate, sodium percarbonate, sodium perphosphate, sodium persulphate and urea peroxide, which release hydrogen peroxide (in the form of perhydroxyl ion) during the wash. Whilst hydrogen peroxide is an efficient bleach above 60°C, the detergent composition usually includes a "bleach activator", such as tetraacetylethylenediamine, in order to obtain efficient bleaching at wash temperatures below 60°C.
  • active oxygen bleaching agents
  • bleaching agents such as sodium perborate, sodium percarbonate, sodium perphosphate, sodium persulphate and urea peroxide, which release hydrogen peroxide (in the form of perhydroxyl ion) during the wash. Whilst hydrogen peroxide is an efficient bleach above 60°C, the detergent composition usually includes a “bleach activator”, such as tetraacetylethylenediamine, in order to obtain efficient bleaching at wash temperatures below 60°C.
  • the bleach activator "activates" hydrogen peroxide by reacting with it to generate another, more efficient, bleach.
  • tetraacetylethylenediamine (1, see Figure 1)
  • the perhydroxyl ion reacts at the N-acetylacetamide moiety to hydrolyse the amide bond (in a process known as perhydrolysis,).
  • the perhydrolysis produces peracetic acid (3, in the form of peracetyl ion) which is a fast-acting and more efficient bleach than hydrogen peroxide at temperatures below 60°C, for example at 40°C.
  • the by-product of perhydrolysis is diacetylethylenediamine (2, DAED), which is biodegradable and removed with wash liquor to the environment.
  • Tetraacetylethylenediamine is commercially manufactured by acetylation of diacetylethylenediamine using acetic anhydride. Crystals of tetraacetylethylenediamine are obtained by filtering the reacted mixture after distillation of the by-product acetic acid (boiling point 118°C) and cooling to room temperature or lower.
  • tetraacetylethylenediamine as a bleach activator arises from its low solubility (1.4 to 2.0 g/1 at 20°C) and low dissolution rate in water.
  • a low availability of tetraacetylethylenediamine during room temperature wash or in (increasingly recommended) rapid wash cycles means inefficient cleaning by incomplete activation of perhydroxyl ion and wastage of tetraacetylethylenediamine .
  • compositions described in WO 2013/171492 Al comprise in excess of three times the amount of triacetylethylenediamine as compared to tetraacetylethylenediamine because triacetylethylenediamine comprises only a single N-acetylacetamide moiety which is susceptible to perhydrolysis and so is inherently a less efficient activator than tetraacetylethylenediamine .
  • the present invention generally aims to address this need by providing a new crystalline form of tetraacetylethylenediamine.
  • the present inventors have found a new crystalline form of tetraacetylethylenediamine which has greater solubility in water and much faster dissolution rate than the known crystalline form of tetraacetylethylenediamine.
  • the new polymorph of tetraacetylethylenediamine is herein designated crystalline "Form ⁇ " of tetraacetylethylenediamine.
  • the hitherto known crystalline structure of tetraacetylethylenediamine (which corresponds to commercial tetraacetylethylenediamine) has now also to be considered a polymorph and is herein designated crystalline "Form I" of tetraacetylethylenediamine .
  • the present invention comprises crystalline Form II of tetraacetylethylenediamine which has solubility in water (pH 7.0) at 20°C and atmospheric pressure above 2 g/1.
  • the present invention comprises crystalline Form II of tetraacetylethylenediamine (TAED) which has absorptions in its Fourier Transform Infra-Red spectrum at wavenumbers 3013 cm “1 , 2979 cm “1 and 2945 cm “1 .
  • TAED tetraacetylethylenediamine
  • the present invention comprises crystalline Form II of tetraacetylethylenediamine having an X-ray powder diffraction pattern measured using Cu (K a ) radiation (154 nm) containing a reflective peak at a 2 ⁇ value corresponding to a distance between parallel planes of atoms of 9.73A.
  • the crystalline Form II of tetraacetylethylenediamine has an X-ray powder diffraction pattern further containing reflective peak at 2 ⁇ values corresponding to the following distances between parallel planes of atoms: 4.97A, 4.90A, 4.81 A and 4.63A.
  • the crystalline Form II of tetraacetylethylenediamine has an X-ray powder diffraction pattern also containing reflective peaks at 2 ⁇ values corresponding to the following distances between parallel planes of atoms: 4.16A, 4.06 ⁇ , 3.73A, 3.64A and 3.17A.
  • the crystalline Form II of tetraacetylethylenediamine has an X-ray powder diffraction pattern as set out in Table 1.
  • the new crystalline form of tetraacetylethylenediamine may be prepared by melt crystallisation of crystalline Form I of tetraacetylethylenediamine.
  • the melt crystallisation may be carried out by heating tetraacetylethylenediamine Form I to a temperature from about 20°C below to about 20°C above its melting point (152°C).
  • the present invention comprises a method for the preparation of crystalline Form II of tetraacetylethylenediamine, comprising heating crystalline Form I of tetraacetylethylenediamine to melting and allowing the molten tetraacetylethylenediamine to solidify to a solid mass by cooling to room temperature.
  • the method further comprises comminuting the solid mass whereby to form particles and/or particulates.
  • the comminuting may, in particular, result in particle and/or particulate sizes of between 10 ⁇ to 20 ⁇ .
  • the heating of crystalline Form I of tetraacetylethylenediamine may, in particular, comprise heating to a predetermined temperature from about 140°C to about 170°C (for example, to 145°C, 150°C, 155°C, 160°C or 165°C).
  • the cooling preferably comprises cooling the molten tetraacetylethylenediamine at room temperature.
  • the predetermined temperature (and/or the rate and duration of the heating) may be selected so that the solid obtained on cooling contains at least 50%, for example 80%, 85%, 90%, 95% or 100% of crystalline Form II of tetraacetylethylenediamine.
  • the heating may be carried by heating crystalline Form I of tetraacetylethylenediamine in any suitable container. It may be effected by simply heating a crucible or by the use of an insulated or electrically heated vessel. Preferably, however, the heating is accompanied by agitation. Suitable equipment for effecting heating and agitation includes single screw and twin screw hot melt extruders, melt granulators, pan mills and high temperature kneaders. The use of such equipment enables crystalline Form II of tetraacetylethylenediamine to be manufactured by a continuous process or by a batch process.
  • additives does not divert or inhibit the formation of crystalline Form II of tetraacetylethylenediamine by the method.
  • a large number of additives are tolerated and even additives which are otherwise well-known as co-crystal formers, such as urea and citric acid, do not affect or alter the formation of crystalline Form II of tetraacetylethylenediamine by this method.
  • the heating of crystalline Form I of tetraacetylethylenediamine is carried out in the presence of one or more additives.
  • the one or more additives are suitable for formulation of a solid composition of crystalline Form II of tetraacetylethylenediamine, for example, as a detergent or bleaching composition.
  • the heating of crystalline Form I of tetraacetylethylenediamine may, in particular, be carried out in the presence of one or more additives selected from the group consisting of a surfactant or wetting agent, a pH modifier, a chelating agent, a stabilising agent, a diluent, a glidant, a binding agent, an effervescing agent, a disintegrating agent and a coating agent.
  • a surfactant or wetting agent a pH modifier, a chelating agent, a stabilising agent, a diluent, a glidant, a binding agent, an effervescing agent, a disintegrating agent and a coating agent.
  • the present invention comprises a solid composition comprising a bleach activator, which bleach activator comprises crystalline Form II of tetraacetylethylenediamine.
  • the solid composition may take the form of granules, pellets, powder or tablet. It may, in particular, take the form of an effervescing tablet.
  • the granules or powder may be provided with a sachet comprising a polymer which dissolves in water.
  • a suitable sachet is described, for example, in United States patent application US 2013/0171264 Al .
  • the % weight of crystalline Form II of tetraacetylethylenediamine in the solid composition may vary depending on the intended use of the solid composition.
  • the solid composition comprises at least 0.1% and preferably less than 20% by weight of crystalline Form II of tetraacetylethylenediamine.
  • the solid composition may, in particular, comprise from 0.5% to 10% or from 0.5% to 8% or from 0.5% to 2.5% or less by weight of crystalline Form II of tetraacetylethylenediamine.
  • the % weight of crystalline Form II of tetraacetylethylenediamine is preferably from 1.25% to 2.5%.
  • the % weight of crystalline Form II of tetraacetylethylenediamine is preferably from 4.0% to 5.0%.
  • the % weight of crystalline Form II of tetraacetylethylenediamine is preferably from 2.0% to 3.0%.
  • the % weight of crystalline Form II of tetraacetylethylenediamine is preferably from 2.4% to 3.5%.
  • Suitable additional bleach activators may, for example, be selected from the group consisting of crystalline Form I of tetraacetylethylenediamine, triacetylethylenediamine, nonanoyloxybenzene sulphonate (NOBS) and dodecanoyloxybenzene sulphonate (DOBS).
  • NOBS nonanoyloxybenzene sulphonate
  • DOBS dodecanoyloxybenzene sulphonate
  • the solid composition also comprises a bleaching agent such as sodium perborate, sodium percarbonate, sodium perphosphate, sodium persulphate or urea peroxide.
  • a bleaching agent such as sodium perborate, sodium percarbonate, sodium perphosphate, sodium persulphate or urea peroxide.
  • the solid composition additionally comprises one or more of a surfactant or wetting agent.
  • the solid composition may be formulated as a detergent composition or for a disinfectant or germicidal solution by selection of an appropriate % weight of the one or more surfactant or wetting agent.
  • the solid composition may also comprise one or more additives selected from the group consisting of a pH modifier, a chelating agent, a stabilising agent, a diluent, a glidant, a binding agent, an effervescing agent, a disintegrating agent and a coating agent.
  • the solid composition includes one or more of a surfactant or wetting agent selected from the group consisting of sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, sodium pareth sulfate, dioctyl sodium sulfosuccinate, perfluorobutanesulfonic acid, perfluorononanoic acid, perfluorooctane sulfonic acid, perfluorooctanoic acid, potassium lauryl sulfate, soap, soap substitute, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium lauroyl sarcosinate, sodium myreth sulfate, sodium stearate, benzalkonium chloride, benzethonium chloride, bronidox, cetrimonium bromide, cetrimonium chloride, dimethyldioctadecyl sodium sulfate
  • the solid composition also includes one or more of a pH modifier selected from the group consisting of monopotassium phosphate, bicarbonate, monosodium phosphate and disodium phosphate, sulfamic acid, urea, citric acid, sodium/potassium silicate, sodium/potassium carbonate and sodium/potassium hydroxide.
  • a pH modifier selected from the group consisting of monopotassium phosphate, bicarbonate, monosodium phosphate and disodium phosphate, sulfamic acid, urea, citric acid, sodium/potassium silicate, sodium/potassium carbonate and sodium/potassium hydroxide.
  • the solid composition also includes one or more of a chelating agent selected from the group consisting of ethylenediaminetetraacetic acid, citric acid, sodium citrate, diethylene triamine pentaacetic acid, nitrilotriacetic acid, zeolite, condensed phosphate, acrylate-based polymers, sodium gluconate and phosphonates.
  • a stabiliser selected from the group consisting of carboxymethyl cellulose, polyvinylpyrrolidone, silicates, phosphates, proteases, amylases, lipases and cellulases.
  • the solid composition also includes one or more of a diluent selected from the group consisting of lactose, starch, sucrose, mannitol, sorbitol, cellulose, in particular, powdered cellulose, microcrystalline cellulose, inorganic materials including calcium phosphates such as anhydrous dibasic calcium phosphate, dibasic calcium phosphate, tribasic calcium phosphate and co- processed diluents.
  • a diluent selected from the group consisting of lactose, starch, sucrose, mannitol, sorbitol, cellulose, in particular, powdered cellulose, microcrystalline cellulose, inorganic materials including calcium phosphates such as anhydrous dibasic calcium phosphate, dibasic calcium phosphate, tribasic calcium phosphate and co- processed diluents.
  • the solid composition also includes one or more of a glidant selected from the group consisting of magnesium stearate, aerosil (colloidal silicon dioxide), starch and talc.
  • a glidant selected from the group consisting of magnesium stearate, aerosil (colloidal silicon dioxide), starch and talc.
  • the solid composition also includes one or more of a binder selected from the group consisting of saccharides and their derivatives, in particular, disaccharides such as sucrose, lactose; polysaccharides and their derivatives including starches, cellulose or modified cellulose such as microcrystalline cellulose and cellulose ethers such as hydroxypropyl cellulose; sugar alcohols such as xylitol, sorbitol or maltitol; proteins such as gelatin; synthetic polymers such as polyvinylpyrrolidone and polyethylene glycol binders.
  • a binder selected from the group consisting of saccharides and their derivatives, in particular, disaccharides such as sucrose, lactose; polysaccharides and their derivatives including starches, cellulose or modified cellulose such as microcrystalline cellulose and cellulose ethers such as hydroxypropyl cellulose; sugar alcohols such as xylitol, sorbitol or maltitol; proteins such as gelatin; synthetic polymers such as poly
  • Preferred binders include gelatin, cellulose, cellulose derivatives, polyvinylpyrrolidone, starch, sucrose and polyethylene glycol and dry binders such as cellulose, methyl cellulose, polyvinylpyrrolidone and polyethylene glycol.
  • the solid composition also includes one or more of a disintegrant selected from the group consisting of cross-linked polymers such as cross-linked polyvinylpyrrolidone (for example, crospovidone), cross-linked sodium carboxymethyl cellulose (for example, croscarmellose sodium), and the modified starch sodium starch glycolate.
  • a disintegrant selected from the group consisting of cross-linked polymers such as cross-linked polyvinylpyrrolidone (for example, crospovidone), cross-linked sodium carboxymethyl cellulose (for example, croscarmellose sodium), and the modified starch sodium starch glycolate.
  • the solid composition also includes one or more of a coating agent selected from the group consisting of cellulose ether hydroxypropyl methylcellulose, hydropropylmethyl cellulose phthalate and hydropropylmethyl cellulose acetate succinate, cellulose acetate phthalate, shellac, corn protein zein or other polysaccharides, gelatine, polyvinyl alcohol.
  • a coating agent selected from the group consisting of cellulose ether hydroxypropyl methylcellulose, hydropropylmethyl cellulose phthalate and hydropropylmethyl cellulose acetate succinate, cellulose acetate phthalate, shellac, corn protein zein or other polysaccharides, gelatine, polyvinyl alcohol.
  • the selection of the one or more additives and their % weight for the solid composition will also depend on whether the solid composition is intended to be used as a detergent composition or for producing a disinfectant solution or a bleaching solution.
  • the solid composition comprises TAED crystalline Form II and urea.
  • the solid composition may be formulated as a powder or a tablet with or without a bleaching agent such as sodium percarbonate. It may also comprise one or more additives, for example, shellac, hydroxypropyl methyl cellulose acetate succinate (HPMCAS), sodium bicarbonate or sodium carbonate.
  • HPMCAS hydroxypropyl methyl cellulose acetate succinate
  • the amount of TAED crystalline Form II in the solid composition may vary between 10% and 95%.
  • the solid composition may, for example, comprise or be based on a 1 : 1 mixture (mole) of TAED crystalline Form II and urea.
  • the percentage amount (by weight) of TAED crystalline Form II in the solid composition may, for example, be about 75%, 80% or 90% or, when a bleaching agent is present, about 20% or 30%.
  • Figure 1 is a scheme highlighting the chemical structure of tetraacetylethylenediamine and the perhydrolysis at the N-acetylacetamide moiety;
  • Figure 2 shows the powder X-ray diffraction patterns of crystalline Form II of tetraacetylethylenediamine and crystalline Form I of tetraacetylethylenediamine;
  • Figure 3 shows the FT-IR spectra of crystalline Form II of tetraacetylethylenediamine and crystalline Form I of tetraacetylethylenediamine;
  • Figure 4 shows Raman spectra of crystalline Form II of tetraacetylethylenediamine and crystalline Form I of tetraacetylethylenediamine;
  • Figure 5 shows DSC thermograms highlighting the melting points of crystalline Form II of tetraacetylethylenediamine and crystalline Form I of tetraacetylethylenediamine;
  • Figure 6 shows the powder X-ray diffraction patterns obtained by a variable temperature powder X-ray diffraction study of the conversion of crystalline Form I of tetraacetylethylenediamine to crystalline Form II of tetraacetylethylenediamine;
  • Figure 7 shows photographs highlighting the crystal habits of crystalline Form II of tetraacetylethylenediamine and crystalline Form I of tetraacetylethylenediamine;
  • Figure 8 a graph showing the rate of dissolution of crystalline Form II of tetraacetylethylenediamine in water at 20°C as compared to the rate of dissolution of crystalline Form I of tetraacetylethylenediamine;
  • Figure 9 shows the powder X-ray diffraction pattern of crystalline Form II of tetraacetylethylenediamine after storage as compared to the X-ray diffraction pattern of crystalline Form
  • Figure 10 shows the powder X-ray diffraction patterns of a composition of crystalline Form
  • Figure 11 is a graph showing the rate of dissolution of a solid composition of crystalline Form II of TAED and urea as compared to that of crystalline Form II of TAED and that of crystalline Form I of TAED.
  • a glass crucible was charged with 500 mg of commercial tetraacetylethylenediamine (Form I, Sigma- Aldrich, UK) and the crucible heated on a hotplate to a temperature of 155°C. After 10 minutes of gentle stirring at 155°C with a glass rod, the tetraacetylethylenediamine formed a molten mass. The crucible was removed from the hotplate and allowed to cool to room temperature. The solid mass of tetraacetylethylenediamine obtained was transferred to a mortar and pestle and crushed (for about 5 minutes) to a fine powder.
  • the screw rotation speed was set to 100 rpm and tetraacetylethylenediamine fed at 0.3 kg/h feed rate to the barrel using a gravimetric twin screw feeder (Brabender, DE).
  • the barrel was heated at a rate of 10°C per minute to a temperature profile shown in Table 2.
  • the extruded material was allowed to cool to room temperature and the granular material so obtained comminuted using an IKA cutter mill equipped with a 1 mm sieve (for 5 minutes) to a fine powder (particle size 10 ⁇ to 20 ⁇ ).
  • Figure 2 shows the powder X-ray diffraction pattern of the melt crystals (Form II) as compared to the pattern obtained using this apparatus for commercial tetraacetylethylenediamine (Form I; particle size 10 ⁇ to 20 ⁇ ) and a library pattern for tetraacetylethylenediamine (Cambridge Structural Database).
  • the pattern obtained for the melt crystals is quite different to the pattern obtained for commercial tetraacetylethylenediamine and the library pattern (Form I; these latter two being identical).
  • the pattern for the melt crystal shows an additional peak as compared to the other patterns for tetraacetylethylenediamine and includes a distinctive peak at 2 ⁇ value 9.08° and a distinctive cluster of peaks between 2 ⁇ values 17° and 19°.
  • melt crystallisation of tetraacetylethylenediamine results in a new crystalline form of tetraacetylethylenediamine (Form II) as compared to the previously known (monoclinic) crystalline form of tetraacetylethylenediamine.
  • a Fourier-Transform Infra-Red spectroscopy by Attenuated Total Reflection (ATR) analysis of the powder of Examples 1 and 2 was performed using a Perkin Elmer 100 FT-IR spectrometer equipped GRAMS/AI software. A diamond crystal was used and absorptions were recorded at a constant crystal pressure over 16 scans in the wavelength range 600 cm “1 to 4000 cm “1 .
  • Figure 3 shows the spectrum recorded for the melt crystals (Form II) as compared to the spectrum recorded in the same way for commercial tetraacetylethylenediamine (Form I).
  • the melt crystal (Form II) shows characteristic absorptions at wavenumbers 3013 cm “1 , 2979 cm “1 , 2945 cm “1 , 1710 cm “1 , 1675 cm “1 , 1425 cm “1 , 1372 cm “1 , 1344 cm “1 , 1316 cm “1 , 1267 cm “1 , 1190 cm “1 , 1040 cm “1 , 1027 cm “1 , 974 cm “1 , 757 cm “1 and 696 cm “1 whereas commercial tetraacetylethylenediamine (Form I) shows characteristic absorptions at wavenumbers 1703 cm “1 , 1677 cm “1 , 1432 cm “1 , 1420 cm “1 , 1381 cm “1 , 1355 cm “1 , 1324 cm “1 , 1266 cm “1 , 1 190 cm “1 , 1038 cm “1 , 1024 cm “1 , 977 cm “1 and 761 cm “1 . [0070]
  • the Raman spectrum for the powder of Examples 1 and 2 was recorded using a ReniShaw Raman Microscope at laser wavelength 785 nm and half power.
  • the laser was focused on the powder with a lOOx objective lens with an exposure rate of 10 times per second and spectral accumulation of 1 second.
  • the backscattered radiation was collected (with removal of cosmic rays) by a high numerical aperture and passed through a confocal aperture to the detection system.
  • Figure 4 shows the Raman spectrum recorded for the melt crystals (Form II) as compared to that recorded in the same way for commercial tetraacetylethylenediamine (Form I).
  • the melt crystals shows Raman shifts at wavenumbers 3011 cm “1 , 3000 cm “1 , 2967 cm “1 , 2943 cm “1 , 2939 cm “1 , 1723 cm “1 , 1681 cm “1 , 1458 cm “1 , 1428 cm “1 , 1374 cm “1 , 766 cm “1 and 649 cm “1 whereas commercial tetraacetylethylenediamine shows characteristic Raman shifts at wavenumbers 3023 cm “1 , 2977 cm “1 , 2946 cm “1 , 2937 cm “1 , 1700 cm “1 , 1683 cm “1 , 1427 cm “1 , 766 cm “1 and 649 cm “1 .
  • the Raman shifts for the melt crystals generally show a tendency towards a lower wave number as compared to the Raman shifts for commercial tetraacetylethylenediamine (Form I).
  • Figure 5 shows the thermogram recorded for the melt crystals (Form II) as compared to that recorded for commercial tetraacetylethylenediamine (Form I).
  • melt crystals show a sharp melting point at 150.54°C whereas commercial tetraacetylethylenediamine (Form I) a minor melting endotherms at 142.92°C and a major melting endotherm at 152.47°C.
  • the conversion can, however, be roughly monitored by variable temperature X-ray diffraction.
  • a Bruker D8 diffractometer equipped with a temperature stage was used with scanning rate at 0.02 ⁇ per 0.5 seconds and heating under nitrogen.
  • a 20 mg sample of commercial tetraacetylethylenediamine (Form I; particle size 10 um to 20 ⁇ ) was heated at 12°C per minute to 160°C and the pattern recorded at 10 minute intervals.
  • Figure 6 highlights the changes occurring in the sample when it is heated from room temperature to 160°C and the melt allowed to cool to room temperature.
  • the pattern recorded before heating (A) corresponds to that of Form I of tetraacetylethylenediamine
  • the pattern recorded at 160°C (B) indicates the molten state of tetraacetylethylenediamine
  • the pattern recorded after the melt is allowed to cool to room temperature (C) corresponds to that of Form II of tetraacetylethylenediamine.
  • the patterns show complete conversion of commercial tetraacetylethylenediamine (Form I) to crystalline Form II of tetraacetylethylenediamine.
  • the conversion can also be roughly monitored by hot stage microscopy.
  • the heating of a sample of commercial tetraacetylethylenediamine (Form I; 5 mgs) was examined on a hot stage microscope (Zeiss AxioPlan Mot Microscope) equipped with a Linkam TMS94 temperature controller.
  • the sample was heated to 150°C at a heating rate of 2°C per minute and the resultant molten mass was cooled to room temperature at 2°C per minute.
  • melt crystals were of an agglomerated granular mass.
  • Figure 7 shows a photograph of the sample taken after the melt has cooled to room temperature as compared to a photograph taken before the heating.
  • melt crystals (Form II) have an elongated rectangular (needle-like) crystal habit whereas commercial tetraacetylethylene (Form I) has a square (box-like) crystal habit.
  • Crystalline Form II of tetraacetylethylenediamine has a distinct crystal habit as compared to crystalline Form I of tetraacetylethylenediamine.
  • Powder samples of crystalline Form II of tetraacetylethylenediamine (prepared at a relative humidity less than 50%) were stored in sealed vessels at ambient temperature and pressure and at 40°C and 75% relative humidity. The samples were periodically analysed by powder X-ray diffraction to determine the presence or not of crystalline Form I of tetraacetylethylenediamine.
  • a powder sample of crystalline Form II of tetraacetylethylenediamine were also exposed to an environment of 90% relative humidity (at room temperature) for 13 hours using a Dynamic Vapour Sorption instrument. The sample was analysed by powder X-ray diffraction to determine the presence or not of crystalline Form I of tetraacetylethylenediamine.
  • Figure 8 shows that the patterns obtained during these studies.
  • the sample stored at 40°C and 75% humidity (B) and the sample exposed to an environment of 90% relative humidity at room temperature (C) show no sign of crystalline Form I of tetraacetylethylenediamine (D).
  • Figure 9 is a graph showing the dissolution of the melt crystals (Form II) as compared to the dissolution of commercial tetraacetylethylenediamine (Form I) under similar conditions. As may be seen, crystalline Form II of tetraacetylethylenediamine shows a much higher dissolution rate (pH 7.0) at both 20°C and 40°C as compared to crystalline Form I of tetraacetylethylenediamine.
  • the dissolution rate of crystalline Form II of tetraacetylethylenediamine appears to be an order magnitude higher than the dissolution rate of crystalline Form I of tetraacetylethylenediamine at 20°C.
  • the amount of thiosulphate used in the titre was related to the actual amount of peracetic acid released by tetraacetylethylenediamine on the basis that 2 moles of thiosulphate correlates to 1 mole of peracetic acid.
  • the amount of peracetic acid released by tetraacetylethylenediamine can be calculated by determining the number of moles of tetraacetylethylenediamine in the aliquot (by dividing gram weight by 20 x molecular weight) and multiplying by the number of moles of peracetic acid released by its hydrolysis by perhydroxyl ion (2 moles). [0104] In this experiment, the amount of peracetic acid released by crystalline Form II of tetraacetylethylenediamine at 20°C was calculated as 83 ppm.
  • Example 2 The method of Example 2 was carried out (at relative humidity less than 50%) as described above but with appropriate mixtures of commercial tetraacetylethylenediamine (Form I) and one or more additives.
  • the additives used included pH modifiers (urea, sulfamic acid and citric acid), a detergent surfactant (sodium lauryl sulphate), a coating agent (shellac), a disintegrating agent (Plasdone®) or a binding agent (polyethylene oxide, PEO).
  • pH modifiers urea, sulfamic acid and citric acid
  • a detergent surfactant sodium lauryl sulphate
  • a coating agent shellac
  • a disintegrating agent Plasdone®
  • a binding agent polyethylene oxide, PEO
  • Citric acid 5 Form II only
  • Citric acid 5 Form II only
  • Figures 10 (a) and (b) show respectively the powder X-ray diffraction pattern for a composition comprising 21% urea (79% crystalline Form II of tetraacetylethylenediamine) and the powder X-ray diffraction pattern for a composition comprising 5% citric acid (95% crystalline Form II of tetraacetylethylenediamine) obtained after 6 months storage under these conditions (C) as compared to the powder X-ray diffraction pattern of the composition on forming (B) and the powder X-ray diffraction patterns of crystalline Form II of tetraacetylethylenediamine (A) and crystalline Form I of tetraacetylethylenediamine (D).
  • compositions comprising TAED crystalline Form II and urea (Table 7) were prepared by a method similar to that of Example 2.
  • the hot melt extrusions were carried out at a temperature 150°C using a 1 : 1 mixture (mole) of TAED crystalline Form I and urea.
  • an additional additive shellac or hydroxypropyl methyl cellulose acetate succinate (HPMCAS) was used with the mixture.
  • a powder X-ray analysis of the powders obtained following the comminution showed that each composition comprised TAED in crystalline Form II.
  • the dissolution was monitored by analysing samples ( ⁇ ) taken at time intervals by high performance liquid chromatography.
  • the analysis (and that of Example 3) was carried out on a CI 8 water symmetry column (4.6 mm x 250 mm; particle size 5 ⁇ ) using acetonitrile and deionised water as the mobile phase (1 : 1 with 0.1% orthophosphoric acid) at a flow rate of 1 mL/minute.
  • the column was equipped with a Waters e-2695 separation module integrated with a degasser and photodiode detector (PDA-2298) employing Empower 3 software for peak analysis at wavelength 260 nm.
  • PDA-2298 degasser and photodiode detector
  • Figure 11 shows the rate of solution of solid composition 1 (c) as compared to that of TAED crystalline Form II (b) and TAED Form I (a).
  • the rate of solution of solid composition 1 is eight times higher than that of TAED crystalline Form 1.
  • Example 2 and 6 The hot melt extrudates described in Example 2 and 6 were comminuted to a particle size of 500 ⁇ using a Kenwood Kmix mini roller compactor.
  • the powders were subjected to tabletting by a RIMEK tablet compressing machined (Mini II MT, 12 station with 4D, 4B and 4BB tooling; Karnavati Engineering Ltd, India) using a 25 mm size punch.
  • Tablets comprising TAED crystalline Form II with sodium percarbonate were formed in a similar manner.
  • the sodium percarbonate was reduced to similar particle size as the comminuted extrudates using an IKA cutter mill and mixed in the ratio 2.5: 1 sodium percarbonate: TAED crystalline Form II in extrudate.
  • the present invention provides a new form of crystalline tetraacetylethylenediamine (Form II) which has at least twice the solubility of commercial tetraacetylethylenediamine (Sigma Aldrich, UK) in water at 20°C and a dissolution rate which appears to be an order of magnitude higher than commercial tetraacetylethylenediamine .
  • the new crystalline form (Form II) offers reduced wastage of tetraacetylethylenediamine across all kinds of laundry, disenfection and bleaching processes and may, therefore, be of benefit to the environment and/or enable cheaper manufacture of solid compositions for these processes by use of less tetraacetylethylenediamine.
  • the new crystalline form (Form II) has good stability and can be easily manufactured from commercial tetraacetylethylenediamine using existing apparatus or equipment in a continuous or batch process and at minimal cost.
  • the method of the present invention is particularly advantageous in that it tolerates the presence of a wide range of additives including additives suitable for the formulation of solid detergent and bleaching compositions. It may, therefore, avoid an extra manufacturing step whilst still obtaining the benefit of enhanced laundry, disenfection and bleaching processes.

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Abstract

Une nouvelle forme cristalline de la tétraacétyléthylènediamine (forme II) est préparée par cristallisation par fusion de la forme cristalline de tétraacétyléthylènediamine (forme I) connue, et est caractérisée, entre autres, par la diffraction des rayons X sur poudre, la spectroscopie infrarouge à transformée de Fourier (FT-IR) et la spectroscopie Raman. La Forme cristalline II de la tétraacétyléthylènediamine présente une haute solubilité ainsi qu'une haute vitesse de dissolution dans l'eau à 20 °C, par rapport à la Forme cristalline I de la tétraacétyléthylènediamine.
PCT/GB2016/053270 2015-10-20 2016-10-20 Forme cristalline ii de la tétraacétyléthylènediamine WO2017068348A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022053784A1 (fr) 2020-09-09 2022-03-17 University Of Bradford Forme cristalline iii de tétraacétyléthylènediamine
WO2022053804A1 (fr) 2020-09-08 2022-03-17 One1Star Solutions Limited Forme composite de tétraacétylènediamine

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0051739A1 (fr) * 1980-11-08 1982-05-19 BASF Aktiengesellschaft Procédé de préparation de tétraacétyléthylènediamine
WO2013171492A1 (fr) * 2012-05-18 2013-11-21 Warwick International Group Limited Activation d'un agent de blanchiment peroxygène

Family Cites Families (1)

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Publication number Priority date Publication date Assignee Title
IT1245724B (it) * 1990-11-09 1994-10-14 Caffaro Spa Ind Chim Procedimento di purificazione della taed

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
EP0051739A1 (fr) * 1980-11-08 1982-05-19 BASF Aktiengesellschaft Procédé de préparation de tétraacétyléthylènediamine
WO2013171492A1 (fr) * 2012-05-18 2013-11-21 Warwick International Group Limited Activation d'un agent de blanchiment peroxygène

Non-Patent Citations (1)

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Title
A. P. N. FRANCHIMONT ET AL: "Sur l'acétylation de quelques acétamides substituées", EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, vol. 30, no. 5, 3 September 1911 (1911-09-03), DE, pages 183 - 185, XP055330674, ISSN: 0370-7539, DOI: 10.1002/recl.19110300504 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022053804A1 (fr) 2020-09-08 2022-03-17 One1Star Solutions Limited Forme composite de tétraacétylènediamine
WO2022053784A1 (fr) 2020-09-09 2022-03-17 University Of Bradford Forme cristalline iii de tétraacétyléthylènediamine

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