DE1966944A1 - 1,4-Diacyl glycolurils prodn - by acylating glycoluril in presence of a Lewis acid catalyst - Google Patents

Abstract

Diacylglycolurils of formula (I): (R1 and R2 are the same 2-10C satd. aliphatic acyl or benzoyl) are prepd. by reacting glycoluril with 2 moles of the appropriate acid anhydride or chloride as acylating agent in the presence of 0.001-0.5 times by wt. of a Lewis acid (esp. H2SO4 or HClO4) at 40-90 degrees C/normal pressure. (I) are intermediates, by further acylation, for cold-bleach activators and, by halogenation, for disinfectants.

Description

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: D 583 ^ -lv : ', -; _ /

"Process for the preparation of 1,4-diacylglycolirpils"

Aussehexdung from the patent application P 1909 A-nraeldedatl lra of the star artefacts: 27 · 2 · 1969 ·

The invention relates to a method of production of 1,4-diacylglycolurils of the general formula V

O = G

in which R 1 and R p ideiitische saturated aliphatic acyl radicals with 2 to 10 carbon substances or benzyl radicals mean> by reaction of glycol with one of the acyl radicals R 1 and R p corresponding carboxylic acid anhydride or chloride, characterized by the fact that 1 mol of glycoluril is marked in the presence of of 0.001 - .to '0, 5-fold overall' weight amount of a Lewi-ssaure as a catalyst in ^J f0 reacting to 90 ⁰ C and at Nor maldruck with 2 moles of Äcylierungsinittels. '- ■ / ". - ■" ■ - ■ - .. _; ν:

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509826/0932

Sheet 2 for patent application D - '! 50 _- O - patent department

Henkel & Cie GmbH

The compounds prepared according to the invention are valuable Intermediates; they can be mixed, for example, by further acylation to give those suitable as cold bleach activators tetraacylated glycolurils of DT-OS 1 909 876, or by halogenation to give the diacyl-dichloro- or dibromoglycolurils which can be used as disinfecting agents of DT-OS-2 025 851 are implemented.

As saturated aliphatic acyl radicals with 2 to 10 carbon atoms for the substituents R, And R ^ ^ e ** general formula unsubstituted and optionally substituted aliphatic carboxylic acid radicals, such as acetyl, chloroeetyl, propionyl, butyryl, isobutyryl, .Caproyl, capryloyl, caprinyl radicals.

Suitable acylation catalysts of the Lewis acid type are, for example, boron trifluoride, zinc chloride and aluminum chloride and especially mineral acids such as sulfuric acid and perchloric acid.

In the process according to the invention, a small excess of acylating agent is generally used; but even with equimolar amounts of acylating agent for each acyl radical to be introduced, good results are achieved. It is preferably 1.1 to 1.5 times the molar amount of carboxylic anhydride or chloride to be introduced for each Acyl radical used. Because of the low solubility of the diacylglycolurils In comparison to the glycoluril and the tetraacylated glycolurils, the process end point is good determine. If, after cooling, the product of the process is removed from any residues of the acylating agent that may still be present separated, then the diacylated glycoluril is in of a purity sufficient for technical use. Any traces of glycoluril or tetra-

509826/093 2 'ORIGINAL BATHROOM

-: ■ - ^ Kenker & CieGmbH

Sheet 3 of the patent application D yo_} jx Patent Department

acylated GlykoTurÜ * can because of their greater solubility Wash lightly with a suitable solvent such as chloroform.

In order to improve the stirrability of the reaction mixture or a to achieve better solubility of the reactants is in some cases it is expedient to add the acylating agent. corresponding free carboxylic acid or another inert solution or diluents such as dioxane, diethylene glycol ■ _dimethyl ether, Add benzene, toluene, xylene, etc.

i, -

The acetylation of glycoluril to 1,3 * 4 * 6-tetraacetylglycoluril is described in the literature (H. Blitz, Ber. Der Deutschen Chemischen Gesellschaft 40, 48o6 - 4816, (1907)). According to the information in the literature, glycoluril is used heated with a 3 '5-fold molar excess of acetic anhydride in the presence of a double with respect to the glycoluril amount by weight of sodium acetate as catalyst for 4 hours under pressure at l40 bisl5O ⁰ C. In contrast, it is surprisingly possible by the process according to the invention, by using the acidic catalysts mentioned in amounts which are 0.001 to 0.5 times, preferably Öj 01 to Ö _y 2 times, the glycoluril used, to diacylate the glycoluril in a targeted manner. The inventive method is also characterized by short response times, etc., mild reaction temperatures xmd normal pressure conditions at} s. A further advantage of the process according to the invention is that the catalyst does not need to be separated off when working up the ethylation product. no special measures are required for this. In general, it is sufficient to separate the solid reaction product from the liquid phase, which may consist of excess acylating agent or the carboxylic acid formed from the acylating agent or a further solvent. As far as-in the subsequent-

the following working examples, the reaction products were crystallized, this was done in order to obtain a purer product for the melting point determination. To the technical Further use of the process products - is a recrystallization however, it is generally not required. "If _

509826/09: 32 :: ■ . bath

Henkel & <3β GmbH

Sheet 4 for patent application D 3833 "" I patent division

'4

I j 4-diacety: lp; lykoluril

The mixture of 142 g (1.0 mol) of glycoluril, 20 g (2.5 mol) of acetic anhydride and 450 ml of glacial acetic acid was admixed with 2 ml of 70% perchloric acid and heated to 85 to 90 ° C. for 4 hours while stirring. After cooling, the solid reaction product is filtered off with suction, washed with chloroform to remove traces of tetraacetylglycoluril and dried. 1,4-diacetylglycoluril was obtained in this way in a yield of 80.5 % ; Melting point: 326-328 ⁰ C. After recrystallization from dimethyl * - ■ formamide was the melting point is 328 to 330 ⁰ C. "

In the use of dioxane (500 ml L) instead of ice, ethyl 1,4-Diacetylglykoluril in 94 $ yield was obtained after a reaction time of 30 min., And at a reaction temperature of 45 ⁰ C.

Example 2 '

1,4-Dip ropionylp; lykq luril

The mixture of 142 g (1.0 mol) of glycoluril and 325 g (2.5 mol) of proponic anhydride was mixed with 2 ml of 70% perchloric acid and heated to 85-90 ° C. for 3 hours with stirring, without any further addition of solvent. After cooling the product was filtered off with suction, washed with chloroform and dried. ™ Melting point of the product obtained in this way: 249-252 ° C; 74.6 % yield.. · "■ " - '.

Examples 3 and 4

Using the appropriate carboxylic acid anhydride the following 1,4-diacylglycolurils were found in an analogous manner obtain: ' . ·

5.09826 / 0932 bad original

.. Henke! &C; e GmbH

Sheet 5 to patent application D 3P ^ "^ ^ - patent department

Example 3: 1.4 "Dibutyrylglycolurll"

Melting point: 228-230 ⁰ Cj. Yield 70.2 #.

Example 4: 1,4-dicapryloylglycoluril; . .

Melting point 186 ⁰ C; Yield 51.0 f ^. _; ν, · .. ■ '■■■. j

Example 5 ... ^{; :} 'τ-'Ί -.:-..-; ';:. .-... 1,4-Dibenzoylglycolur 11: "■ _ '_; /-.= ■ -..- ■

The suspension of 14.2 g (0.1 mol) of glycoluril and 68 g; (0.3 mol) of benzoic anhydride in 140 ml of Dloxan was mixed with 2.5 iwl of 100% Pei ^ chloric acid and heated to 90 ° C. for 10 hours -.- After cooling, the reaction product was filtered off with suction, washed with chloroform and dried . The so obtained l, 4 ~ Dibenzoylglykoluril melted by TJmkristallisieren from dioxane / dimethylformamide at 294; ~; 296 ⁰ Cj yield: 64 $. :; · ".

Example 6 ^:

1,4- di- (chlor ace

This compound was prepared using chloroacetyl chloride and perchloric acid as a catalyst. Yield: 73 '5%''Meltingpoint:> 360 ⁰ C / ^v ----- ._ ";"' _ ■. _ä: ..--. "■ -

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509826/0952

Claims (2)

"Process for the preparation of 1,4-diaeylglycolurils of the general formula. O = C G = O in which R ₁ and R _{2 are} identical saturated aliphatic acyl radicals having 2 to 10 carbon atoms or benzoyl radicals, by reacting glycoluril with one of the. Acyl radicals R, and R ₂ corresponding carboxylic acid anhydride or chloride, characterized in that 1 mol of glycoluril in the presence of 0.001 to 0.5 times the amount by weight of a Lewis acid as a catalyst at 40 to 90 ° C and at normal pressure with 2 mol of the Acylierungsm .implemented by means of. 2. The method according to claim 1, characterized in that sulfuric acid or perchloric acid are used as catalysts. . >. Method according to claims 1 and 2, characterized in that that for each acyl radical to be introduced the corresponding one Carboxylic acid anhydride or chloride is used in 1.1 to 1.5 times the molar amount. k. Process according to Claim 1 "- j5> characterized in that the acylation is carried out in the presence of the free carboxylic acid corresponding to the acyl radical or another inert solvent or diluent. 509826/0932 BATH ORIGINAL