DE2351297A1 - Di-chloromethyl-acrylamide and -methacrylamide prepn - by reacting acrylamides with formaldehyde or formaldehyde precursors and acid chlorides - Google Patents

Abstract

Novel N,N-Di-(chloromethyl)-acrylamides having formula CH2 = CRCON(CH2Cl)2 (I) (where R is H, Me or Et) are prepd. by reacting acrylamides having formula CH2 = CRCONHR1 (II) (where R1 is H, HOCH2- or lower alkoxymethyl) with HCHO or HCHO-yielding cpds. and organic or inorganic acid chlorides, pref. thionyl chloride, pref. in presence of acid binders. (I) are intermediates for organic syntheses, e.g. prepn. of auxiliaries for textile, dyeing and printing industry, prodn. of plant protective agents, surfactants and polymerisable monomers. (I) react with long chain gp. -contg. tert. amines to form NH4 cpds. used for wash-resistant softening and anti-static finishing of textiles, as such or as copolymers with other unsatd. monomers.

Description

Bayer Aktiengesellschaft 2351297

Central area of patents, trademarks and licenses

B / HM 509 Leverkusen, Bayerwerk

10. OM. 1973

^, N-bishalomethyl-acrylamides

The invention relates to new N, N-bis (chloromethyl) acrylamides the formula

^ CH ₉ Cl

CH ₉ = C-CO-N ^ά - I,

^ά \ ^ CHCl

in which R represents hydrogen, a methyl or ethyl radical, in particular the methyl radical, and a process for their Manufacturing.

The compounds of formula (I) are prepared by using acrylamides of the formula

CH ₉ = C-CO-N II

i ^X1

in which R has the abovementioned meaning, and S ^{1 is} hydrogen, a hydroxymethyl or lower. Alkoxymethyl group is reacted with formaldehyde or formaldehyde-releasing compounds and organic or inorganic acid chlorides.

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Examples of starting compounds of the formula II are acrylamide, N-hydroxymethyl-acrylamide, N-methoxymethyl-acrylamide, Methacrylamide, N-hydroxymethyl methacrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl methacrylamide, N-isopropoxymethyl methacrylamide or N-hydroxymethyl-ethacrylamide called.

The formaldehyde can be used in the gaseous state or in the form of aqueous solutions, in the latter case In the event that the water must be completely removed before the further reaction with acid chlorides. Advantageously However, instead of the free formaldehyde, formaldehyde-releasing compounds such as paraformaldehyde, trioxane or Formaldehyde dimethyl acetal is used.

The organic acid chlorides usually used to substitute the hydroxyl group with chlorine can be used as acid chlorides, such as acetyl chloride, oxalyl chloride or phthaloyl chloride, or inorganic acid chlorides such as phosphorus trichloride, Phosphorus oxychloride, phosphorus pentachloride or especially thionyl chloride can be used.

The reaction can be carried out in such a way that the acrylamides of the formula II, where appropriate, basic in the presence of catalysts such as alkali metal hydroxides, for example sodium or potassium hydroxide, releasing with formaldehyde or formaldehyde compounds at 50 - condensed 150 ⁰ C and the obtained products slowly at -10 to 80 ⁰ C mixed with the acid chloride, or slowly added to the acid chloride. If acrylamides of the formula II are used, in which R stands for a hydroxymethyl or an alkoxymethyl group, at least 1 mol, preferably 1.2-2 mol of formaldehyde is used per mole of arylamide of the formula II. Using

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at least 2 moles of unsubstituted acrylamides are used, Preferably 2.2-3 moles of formaldehyde per mole of acrylamide. The acid chlorides are used in at least a 2 molar amount ("based on acrylamide of the formula II), preferably in 2.2 up to 3 times the molar amount used.

However, you can also carry out the implementation in the way, that you have the acrylamide of formula II and the corresponding Amount of a formaldehyde-releasing compound mixed together and then without prior condensation with the acid chloride brings to implementation «

In a preferred embodiment, methacrylamide, N-hydroxymethyl-methacrylamide or N-methoxymethyl-meihacrylamid at 70-120 ⁰ G _9, optionally in the presence of basischei catalysts with paraformaldehyde or trioxane, and the condensation product obtained at -10 to + 4O ⁰ C slowly added to thionyl chloride

The reaction with formaldehyde and the acid chloride can optionally be carried out in order to ensure the stirrability of the reaction mixture to improve, in a diluent inert under the reaction conditions, such as hydrocarbons, halogenated Hydrocarbons, dimethylformamide, diethyl ether, Dioxane or tetrahydrofuran can be carried out.

To prevent polymerization reactions are employed the reaction mixtures advantageously usual polymerization inhibitors such as hydroquinone, phenothiazine u _o a _o, in small amounts to "

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To achieve purer products, it is advantageous to add the reaction batches before or after the reaction with formaldehyde, add inorganic or organic acid binders. These will, especially when using thionyl chloride used as acid chloride, preferably in an amount equivalent to the amount of acid released. Suitable inorganic Acid binders are, in particular, oxides, hydroxides or carbonates of alkali or alkaline earth metals, e.g. B. Potassium or sodium carbonate, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide or Magnesium carbonate. As organic acid binders are for example tertiary amines, such as triethylamine, tributylamine, Dimethylcyclohexylamine, dimethylbenzylamine or pyridine called.

In some cases it can be advantageous to add water-binding agents, e.g. potassium carbonate, Add sodium sulphate, calcium chloride or silica gel to prevent any water that may have formed from reacting with the To prevent bis-chloromethylamides.

It is known from Belgian patent specification 621 378 that N-chloromethyl-N-methyl-methacrylic acid amide can be reacted of methacrylic acid chloride with 1,3,5-trimethyl-hexahydro-s-triazine can produce. However, the yields are only moderate and the compounds of the formula I can be according to this Process not establish. Furthermore, the German Offenlegungsschrift 1,768,983 describes the production of Ν, Ν-bis-chloromethyl urethanes by converting bis-hydroxymethylcarbamic acid esters described with acid chlorides. However, the manufacturing method according to the invention was also achieved by this method not suggested, since acrylamides contribute to the formation of bis-hydroxymethyl compounds to a far lesser extent

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tend than this is the Pall in carhamic acid esters, and in addition, an addition of the hydrogen chloride released during the reaction to the double bond can be expected had to. For example, in Houben-Weyl, "Methods of Organic Chemistry ", 4th Edition, Vol. V / 3, p. 822, describes that the addition of hydrogen chloride is particularly easy takes place on the double bond of acrylic acid and its functional derivatives. It is therefore surprising that the compounds of the formula I can be prepared in good purity by the process described.

The new bis-chloromethyl-acrylamides of the formula (I) are valuable intermediate products for organic syntheses, e.g. for the production of auxiliaries for textile, dyeing and printing industry, for the production of plant protection products, surface-active agents and polymerisable products Monomers. They are suitable e.g. for implementation with long-chain Tertiary amines containing residues, e.g. N, N-dimethylstearylamine, to quaternary ammonium compounds. these can Can be used for wash-resistant, softening and antistatic finishing of textile materials by adding them on the textile materials and fixed them by alkali treatment on the fiber or by radical donating Catalysts or high-energy rays polymerized on the fibers and / or grafted onto them. In addition, these by co-polymerization with other unsaturated monomers textile finishing agents with which are excellent Achieve wash-resistant antistatic and plasticizer effects.

The parts given in the following examples are parts by weight, unless stated otherwise.

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example 1

172 parts of N-methoxymethyl-methacrylamide are mixed with 0.67 parts of powdered potassium hydroxide and 0.67 parts of hydroquinone and 48 parts of paraformaldehyde are added in portions ^{at 70 ° C. The mixture is heated to 110 °} C. and ½ at this temperature hour. The resulting reaction mixture is allowed to now "at 40 ⁰ G to a solution of 357 parts of thionyl chloride in 200 parts by volume of methylene chloride dropwise over 3 hours. 5 parts of paraformaldehyde are added and the mixture is stirred at 40 ^° C. for 2 hours. After cooling to room temperature, the reaction solution is freed from small amounts of a precipitate by suction and ^{concentrated at a temperature of 40 °} C. in vacuo to 1.5 torr. The residue is distilled over a thin film evaporator at 145 ^° C. and 2-3 torr. There will be 117 parts of the connection

/ CH ₉ Cl
CH ₉ = C-CO-N *

CH

obtained as a colorless liquid.
C ₆ H ₉ Cl ₂ NO (Ma = 182) η ^ = 1.4989

Calc .: C 39.5 1 ° H 4.95 5 & Cl 39.0 fo N 7.7 1 ° Found: C 38.8 <fo H 4.8 <fo Cl 38.5 $ N 7.7 ^e />

Example 2

850 parts of methacrylic acid, 800 parts of dioxane, 2,020 parts of triethylamine and 20 T.eile powdered potassium hydroxide are mixed and stirred at 70 - 8O ⁰ C with 660 parts para-

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formaldehyde added. The reaction mixture is stirred for 1/2 hour, cooled, and "at 4-0 -. 50 C to a solution of 2380 parts of thionyl chloride in 2,000 parts by volume of carbon tetrachloride in 24 hours dropped It is further 3 hours at 50 - 55 ⁰ C and stirred for 8 hours at 70 ⁰ O, cooled and filtered off with suction from the precipitated salt the Piltrat is concentrated in vacuo, and a thin-film evaporator at 120 -.. distilled 130 ⁰ C and 1-3 Torr are ^ 420 parts of the product described in example 1 obtain.

Example 3

115 parts of N-methoxymethyl acrylamide are mixed with 2 parts of powdered potassium hydroxide and 0.4 parts of phenothiazine and 31 parts of paraformaldehyde are added at 60-70 °. The mixture is stirred for 1/2 hour at this temperature and then simultaneously added dropwise with 101 parts of triethylamine from various dropping funnels to a solution of 238 parts of thionyl chloride in 300 parts by volume of carbon tetrachloride. The temperature is kept at 40-50 ° C. during this process. The mixture is stirred for 15 hours at this temperature, the reaction mixture is cooled to room temperature and the precipitated salt is filtered off with suction. The filtrate is concentrated in vacuo, and a thin-film evaporator at 150 - distilled 160 ⁰ C and 1-2 Torr. There will be 42 parts of the connection

CH ₂ = CH-CO-I

obtained as a colorless liquid.
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C ₅ H ₇ Cl ₂ NO (MW 168) n ^ ⁰ = 1.5132

Calc .: C 35.7 H 4.17 Cl 42.2
Found: C 34.5 H 4.3 Cl 41.5

Example 4

774 parts of N-methoxymethyl-methacrylamide are mixed with 3 parts of powdered potassium hydroxide and 3 parts of hydroquinone, and then set at 7O ⁰ C with 216 parts of paraformaldehyde. The mixture is heated 15 minutes at 90 ⁰ C, cooled to 40 ⁰ C and allowing the product from separate dropping funnels, at the same time with 1,700 parts of thionyl chloride to a 5 - 1O ⁰ C cooled suspension of 340 parts of anhydrous, drop powdered potassium carbonate in 800 parts of tetrachloromethane. The mixture is stirred for 14 hours at room temperature, heated to 40 ° C. until the evolution of gas has ceased and the salt residue is then filtered off with suction. The filtrate is concentrated in vacuo and distilled over a thin-film evaporator at 140 ^° C. and 2 Torr. 480 parts of the product described in Example 1 are obtained.

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Claims (7)

Patent claims 1. N, N-bis (chloromethyl) acrylamides of the formula CH ₂ = C-CO-II ^ά
R ^ CH ₂ Cl in which R stands for hydrogen, a methyl or ethyl radical. 2. NjN-bis-chloromethyl-methacrylic acid amide 3. Process for the preparation of Nj, N-bis (chloromethyl) acrylamides the formula .CH ₉ Cl
CH ₀ = C-CO-Ii ^{ά R} CHCl in which R stands for hydrogen, a methyl or ethyl radical, characterized in that acrylamides of the formula CH ₀ = C-CO-N
R. in which R has the meaning given above and R is hydrogen, hydroxymethyl or lower Alkoxymethyl group, with formaldehyde or formaldehyde donating compounds and organic or converts inorganic acid chlorides. Le A 15 308 - 9 - 509817/1126 4. The method according to claim 3, characterized in that the reaction with the acid chlorides in the presence of acid binders. 5. The method according to claim 3 and 4, characterized in that the reaction with the acid chlorides at temperatures from -10 to 80 C. 6. The method according to claim 3 to 5, characterized in that that thionyl chloride is used as the acid chloride. 7. The method according to claim 3 to 6, characterized in that one methacrylamide, ΪΓ-methylol-aerylamide or N-methoxymethylacrylamide with formaldehyde or formaldehyde-releasing compounds and thionyl chloride. Le A 15 508 - 10 - 509817/1 126