DE2038106A1 - Activators for per compounds - Google Patents

Description

Henkel & CIe GmbH Düsseldorf, July 28, 1970 '

Patent department -Henkelstraße 67 _on0oinc

Dr. Na / Ma 20381

. Patent application

D 4172
"Activators for Per Compounds"

Aqueous solutions of inorganic per-compounds, in particular hydrogen peroxide or perborates, are since a long time as g oxidation and bleaching agents for a wide variety Materialien.verwandt. However, the active oxygen only becomes effective at temperatures above 70 ° C. and preferably in the range from 80 to 100 ° C. at a rate sufficient for practical purposes, so that these bleaching agents cannot be used with temperature-sensitive materials that are used with regard to the material to be bleached relies on working at relatively low temperatures.

It has already been proposed to add certain N-acyl compounds to the aqueous solutions of per compounds in order to activate the latter. According to DAS 1 162 967, 4 | Compounds are used which have at least two acyl groups attached to the same nitrogen atom, such as Ν, Ν, Ν ¹ -triacetylmethylenediamine, Ν, Ν, Ν ¹ , NV-tetraacetylmethylenediamine and the like. According to DAS 1 281 317, compounds of the general formula RCO-NFU-OCR-j, in which R and RJ are CL ^ -alkyl radicals, are used for this purpose, while Rp can represent any organic radical which, with the formation of an optionally substituted caprolactam-, N-acylated barbitone, phthalimide, anthranil, N-acylated hydantoin or saccharine ring can be combined with R ^. fa

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109 887/1591

Henkel & CIe GmbH s «it» 2 * ur Patomanmeidune D 4172

The Swiss patent specification 478 906 describes the use acylated glycolurils of the general formula

^R 1 ^R 2

• Ν CH-Nv

O = C

C = O

^S N CH N '

wherein at least two of the radicals R ^ to R ^ represent acyl radicals with 2 to 8 carbon atoms, while the other radicals are hydrogen atoms and / or alkyl or aryl radicals with 1 to 8 carbon atoms and / or acyl radicals with 2 to 8 carbon atoms mean as activators for per compounds. The acyl radicals present in a molecule can be identical or different. Tetraacylglycolurils with identical Cp A acyl radicals, in particular tetraacetylglycoluril, are preferably used. ^

109887/1591

Henkel & Cie GmbH su 3 m Pot.rf _O i, m.idun _e d 4172

The invention relates to the use of diacylated 2,5-diketopiperazines the formula

wherein R and Rp optionally substituted hydrocarbon radicals having 1-8 carbon atoms, R, and R ^ optionally substituted hydrocarbon radicals having 1 -3 carbon atoms sawn \ indicate, as activators for HPOP or water HgOp delivered per compounds.

These activators are distinguished from the known ones by a better activating effect.

Diacyl-diketopiperazines with the same radicals R ^ and Rg are easier to produce than those with dissimilar acyl radicals, therefore the former are of greater practical importance. If the radicals R ^ and Rp are aliphatic in nature, they preferably have 1-3 carbon atoms; If it is an aromatic residue, it can contain up to 8 carbon atoms. Accordingly, λ as radicals R and R- are preferably the following: methyl, ethyl, n- or i-propyl, phenyl, toluyl or xylyl radicals. Possible substituents are C 1-4 alkoxyl groups, halogen atoms, nitro or nitrile groups; As an example of the chlorine- and / or nitro-substituted aromatic radicals which are of particular practical interest, m-chlorine or m- or p-nitro-substituted radicals may be mentioned. The radicals R ^ and R ^ are preferably of the same type; there are, for example, the methyl or ethyl radicals optionally substituted by hydroxyl groups, halogen atoms, nitro, nitrile, methoxyl or ethoxyl groups

109887/1591

Henkel & CIe GmbH S.lle 4 for patent application D

Of the aoylated to be used as activators according to the invention Diketopiperazines are the diacetyl and dibenzoyl derivatives from the "Reports of the German Chemical Society" 20 (1897) * page 1585 or £ 4 (192.1), page 2691 known. These compounds are obtained by acylating the diketopiperazine with the corresponding carboxylic acid anhydrides or carboxylic acid halides.

Those in the j5- and / or 6-position can be alkylated in an analogous manner Acylating Diketopiperazines »Die As Starting Materials to be used alkylated piperazines are according to "Bulletin de la Societe Chimique de France ", 1942, - pages 487.- 494 accessible by condensation of the corresponding amino acids. The 3,6-dimethyl-2, .5-diketoplperazine can according to "Recueil des Travaux Chimiques des Pays-Bas "2 £ (1908) page 205 acetylated will.

According to such a procedure, for example, »are available? Dipropionyl-j, Dibutyryl, di-nitriloacetyl., Di-monochloroacetyl., Di-dichloroacetyl, Di-trichloroacety-, di-m-chloro-benzoyl-j, di-nitrobenzoyl-, Di-methoxy-benzoyl- or di-nitrilobenzoyl-diketopiperazine or the corresponding ^ in the 3- and / or 6-position alkylated derivatives.

Dipropionyl-diketopiperazine is obtained, for example, according to the following procedure: A suspension of 22.8 g is stirred (0.2 mol) 2,5-diketopiperazine in 35Ο ml (2.7 mol) proponic anhydride For 3 hours at 140 C. After cooling down, be filtered off undissolved components and evaporated the clear piltrate in vacuo. The crude 1 ^ -dipropionyl ^^ - diketopiperazine obtained in this way can already be used in this state as an activator for per compounds. It can be removed by washing with water, and isopropanol and subsequent recrystallization from iso-, i / ^

- - - 5 -109887/1591

Henkel & Cie GmbH s »\ u 5« "· Patent application ο 4172

ι ■ ■■■■ '

clean propanol. It is then obtained in a yield of 23.5 S j the melting point is at 113 (52.7 fo of theory..) - 114.5 ⁰

The analytical values calculated for the _{empirical formula C 1} Ql-LhN ₂ O ₁ were in satisfactory agreement with the values found. (C calc .: 53.09 %> found : 53.26 % \ H calc .: 6.24 $, found: 5.94 $; N calc .: 12.38 #, found: 12.49 ^ J the IR, NMR and mass spectra agreed with those to be expected for dipropionyl-diketopiperazine.

For the production of 1,4-dipropionyl-3,6 ~ dimethyl-2,5-diketopiperazine a suspension of 28.4 g (0.2 mol) of 3,6-dimethyl-2,5-diketopiperazine in 130 g (1 mol) of propionic anhydride is added with 0.5 ml of 70% perchloric acid and heated to 120-125 ° C. for 8 hours. The clear solution obtained is concentrated and digests the crude dipropionyl-dimethyl-diketopiperazine obtained as a residue with gasoline (bp 80-110 ° C) sucks off and washes the residue again with gasoline. The raw product is obtained in a yield of 14.8 g (29.3 d · Th.) «The melting point is 106-114 ° C. It can be used in this Use texture as an activator. After recrystallization from isopropanol, the analytically pure product melts 113 - 114 ° C.

The analytical values for the ^{empirical formula σ -ιρ Η} -ι8 ^ 2 ^ 4 ^ ^{61 '60} " ¹¹ ® ^ ⁶¹¹ agreed with the values found (C calc .: 56.68 ^, found: 56.59 % i H calc .: 7i15 % » found 7 * 23 #; N calc .: 11.02, found: 11.13 % l) .

109887/1591

Henkel & ClQ GmbH

Soito 6 for Polanlanmldung D

Among the peroxides to be activated, hydrogen peroxide practically plays the greatest role «, It can be used as such, but also in the form of its mostly solid peroxyhydrates or addition products with inorganic and organic compounds. The latter include, for example, the addition products of hydrogen peroxide with urea or Melamine Peroxyhydrates include 3 "B _# the perborates, perortho-, perpyro-p perpolyphosphates, percarbonates and persilicates. The activators according to the invention can, however, also be used together with salts of real peracids, such as, for example, Caro ⁵ acid (peroxomonosulfuric acid H ₂ SOc) or peroxodisulfuric acid (HgSpOg).

Every acyl residue present in the activator is capable of an active ", to activate oxygen atom of the applied per compound; for a complete activation of the active oxygen used Theoretically, the activator and the peroxy compound are therefore to be used in equivalent amounts «, In many Practical cases can also be reached with essentially Smaller amounts of activator have satisfactory effects, while on the other hand the activator can generally also be used in relatively large excesses the amount of activator applied is 0.5 to 6, preferably 0.75 to 5 acyl radicals per active oxygen atom are «// ^

109887/1591

Henkel & Cie GmbH SU 7 lur Palanlanmetdung O 4172

The acceleration of the bleaching or oxidation process is shown both at low temperatures in the range from 20 ° to 70 ° and preferably iron 30 ° to 60 ° C, as well as when this temperature limit is exceeded, which can go up to 95 ° C. The specialist has depending on the problem to be solved the possibility of using of the activators according to the invention either to lower the treatment temperature and / or the treatment duration constant temperature. Finally, you can also have a low and high temperature bleach in one Combine operation. In such cases, | Be part of the goal to use the activator in sub-surplus amounts; only part of the active oxygen present is then activated at low temperatures, the rest is available for bleaching at elevated temperatures ^ .. ■ * ■■ '■'

The conditions to be observed when working with the activators according to the invention, such as, for example, concentration of the peroxide, temperature, pH value and duration of the treatment, depend essentially on the substance to be oxidized or bleached and, if appropriate, on the carrier material on or in which the substance to be bleached is located. The mostly aqueous oxidizing or bleaching liquids can contain 20 to 500, preferably 50 to 250 mg / l of active oxygen and have a pH in the range from 7 to 15, preferably 7-5 to 12 and in particular from 8 to 11. / [/ ^

109887/1591

Henkel & Cie GmbH ε-jiie O zur PntaitanmoMung D 4172

The activators according to the invention can be used wherever peroxy compounds, in particular Hydrogen peroxide or perborates, as Oxidationsbzw. Used bleach. This applies, for example, to the Bleaching of oils, fats and waxes, in cosmetic hair and skin treatment, during disinfection or sterilization, in the passivation of aluminum or other light metal surfaces and especially in the bleaching of Fibers of all kinds.

The desired pH value becomes neutral by adding acidic or alkaline reacting substances, possibly adjusted by buffer devices, above all by additives, which has also been used in a corresponding treatment that has hitherto been customary.

These often include those for reducing surface tension the aqueous oxidation or bleaching liquid serving surface-active substances, such as soap or synthetic detergent active substances known per se, anionic, nonionic, zwitterionic or kati- ■ onic nature. If you work in the alkaline range, alkaline substances and inorganic substances can be added or organic complexing agents, especially for binding the so-called hardness builders in water or any existing ones Heavy metals suitable complexing agents. , 4 /, ^

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109887/1591

Henkel & Cie GmbH sen «9 «> r patent application-.ο 4172

Examples

The usefulness of the invention to be used Activators were demonstrated by the following general experimental methodology.

Aqueous solutions containing 0.615 g NaBO ₂ ^ HgOg.3 H ₂ O (4 mmol) and 2.5 g of Na ^ P ₂ O ₇ .10 H ₂ O contained per liter, were after heating to 45 ° or 60 ° C with 4 mmol of activator ■ added and during the whole experiment with stirring f

kept at the specified temperature. 100 ml "were pipetted off at certain time intervals, immediately on a Mixture of 250 g of ice and 15 ml of glacial acetic acid and then after adding about 0.35 g of potassium iodide with 0.1 η sodium thiosulphate solution and starch titrated as an indicator.

Consumption is made under the specified test conditions with 100% activation of the peroxy compound used approx. 8 ml of thiosulfate solution, in the tables is both the thiosulphate consumption and the percentage Amount of activated peroxy compound indicated.

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109887/1591

Henkel & Cie GmbH

Suite IO to 'patent application D * ■ [ I (C.

Example 1:

Activation of perborate with 1,4-diaoetyl-2,5-dicotopiperazine

sampling
after
χ minutes 0.1 at
ml
η Na ₂ SgO 4th
3 Scored
5 ° c
% 0
activated Al Il O-
! I VO ⁰ C
% 0
activated 1 7.90 97.5 95.2 5 7.67 94.7 90.2 10 7.42 91.6 71.0 15th 7.21 89.0 62.2 30th 6.69 82.6 33.8 60 5.54 68.4 18.5 Blank value 8.10 100 100 establishment
at
, ml
0.1 η Na ₂ S _? 0- 7.62 7.22 5.68 4.98 2.70 1.48 8.00

Example 2:

Activation of perborate with 1,4-dipropionyl-2,5-dlket.opiperazine

sampling
after
χ minutes 0, at
ml
1 η Na ₂ S ₂ O 4!
3 Scored
fo 0
activated Al 60 ° C
% 0
activated χ = 1 7.46 92.1 93.6 5 7.15 88.3 90.0 10 7.07 87.3 77.4 15th 6.91 85.3 66.0 50 6.5? 80/6 40, Q 60 5.78 16.3 Blank value ⁺ 8.10 100 100 <activation
at
ml
0.1 η Na ₂ S ₂ O, ■ 7.48 7.20 6.20 5.28 3.20 1.30 8.00

-Aktivsauersfcoffhalt-der Tastlösungeii ¥ pr Eugabe des Aktiv-

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Henkel & Cie GmbH

Sello 11 mr Pct-.wlunmsldung D4 172

Example ^;

Activation of perborate with 1, H-Di

sampling

after
χ minutes

Achieved activation

at 45 C

ml

0.1 η

activated

at 60 ° C

ml
η Na ₂ S ₂ O,

activated

5
10

15th
30th
60

4.26 7 * 05 6.89 6.58 5.64 4.17

52/0 86.0 84.0 80.2 68.7 50.9 5.7.3 6.04 4.64 3.81

2.15 0.76

69.9 73> 6 56.6 46.6 26.2 9.3

Blank value

8.10

100 8.20

100

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109887/1591

Henkel & Cie GmbH suit «. 1 2 «r Patoniomn» itiunn ο 4172

As can be seen, when using diacetyl- or diproplonyl-diketopiperazine, one already reaches after one Test duration of one minute the maximum degree of activation, which depends on the selected temperature is practically maintained over a certain period of time. The subsequent drop in values is due to the Self-decomposition of the peracetic acid formed primarily. When diacetyl-dimethyl-diketopiperazine increases the amount of activated oxygen slowly increases in the course of the experiment; but it is at after 60 minutes 60 ° C still existing amount of active oxygen "greater than for diacetyl-diketopiperazine «The products differ accordingly in the timing of the activation, and you have the opportunity to choose an activator, its Effect is optimally adapted to the respective bleaching or oxidation process.

These solutions can be used in the most varied areas of technology as oxidizing and bleaching liquids; they also have good antimicrobial properties. ■

If one uses active oxygen per g-atom in the experiments described only 0.5 mol of activator is achieved activation is less, but for many technical purposes it is quite satisfactory. /.. ';;,

109887/1531

Henkel & Gis GmbH s .; ta "13 ^{Iur l> ot} * ^llta "' ⁿ » ^ldlin 9 ^D 4172

Example 4;

For bleaching hair, for coloring hair with the help of oxidizing dyes and aur oxidative post-treatment of hair after shaping under the action of reducing thio compounds (cold wave method), aqueous solutions containing _{10 to 200 g / l H Q 0 are usually used.} Leads

■■■■. . cu £

If these treatment after addition of 20-5 ⁰⁰ g / l or by Diacetyldiketopiperazin dipropionyl-diketopiperazine, a substantial enhancement of the oxidising effect is observed of HPOP, so that, if desired, operate at lower HgO ₂ concentrations kann./ / t _u

- 1A -

109887/1 591

Claims (7)

Henkel & Cie GmbH s.it. 14 to the godfather "tanm" id <.n _e o <4I72 Claims 1. Use of diacylated 2,5-diketopipera2ine of the formula ^R 1 and R- * COR ₁
i ¹ 0 Γ C II O ^ t wherein R ₂ BB ; f. sub £ 3t · Substituted hydrocarbon radicals with 1-8 carbon atoms and R or R ₁ . Hydrogen and / or optionally substituted hydrocarbon residues with 1-5 G atoms, as activators for H ₂ O ₂ or in water H ₃ Q ₂ supplying per compounds 2. Use of diacylated Dikdtqpiperazlne according to claim I ₄ whose acyl radicals contain 2-4 G atoms, as Aktiyatiören fiir Perverbindungen * 3. Use of diacetyl or
in which FU and Rj ₁ methyl radicals u ^ d / or ■ j as activators for Berverbindungen, 4. Use of diaGylated Dikstopiperazfne Räch A ^ pruch 1 to 3 as activators for per compounds Χχ \ an amount of 0.5 to 6, preferably 0.75 to 3 acyl radicals perP AJcti ^ oxygen atom. 5. Use of diaoylated diketopiperazines according to claims 1 to 3 as activated compounds for JPerverbin4un ^ en in oxidation or bleaching liquids _for the 20 |? Is pQQ, ¥ prg; tigsvfeis, e 50 to 250 mg / 1 ftktivsauerstqff · contain. / J ^ 15 - 10 9 8 8 7/1591 Honlcol & Cie GmbH s ^ i »1 5 ^zur p <n * n» oniMi <iung ο 4172 6. Use of diacylated diketopiperazines according to claim 1 to 2 as activators for per compounds in aqueous solution genes with a pH value of 7 to 1% *, preferably 7/5% 12 and especially from 8 to 11, 7. Vervienduriß diacylated dikefcopiperazines according to claim 1 up to 3 as activators in oxidizing hair treatment .. (4 109887/1591