DE1643366A1 - Process for the production of phenol half-formals - Google Patents

Description

FARBENFABRIKEN BAYER AG

LEVERKUSEN- ·· * «!» · * 3 · 10. 1967 Patent department B / M

Process for the production of phenolic semi-formals

The invention relates to a process for the production of phenol half-formals. The procedure is characterized by that one mixes of phenols and aqueous Poröaldehydliösungen heated with stirring to a maximum of 80 ° C and the phenol half-formals formed are then isolated.

In general, it works best to use the mixtures 0.5 to 5 hours, preferably 1 to 2 hours, heated to 30 to 80 ° G, preferably to 40 to 60 ° C, with stirring.

The phenol half-formals formed can be isolated in various ways. So you can think of it as organic Separate phase from the reaction mixture separating phenol half-formals from the aqueous phase. As special However, it has proven advantageous to isolate the phenol half-formals by removing the water the reaction mixture is distilled off in vacuo at temperatures below 80 ° 0.

Examples of phenols that can be used in the process according to the invention are:

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Phenol, alkylphenols, such as cresols, xylenols, 2-ethylphenol, 2,6-diethylphenol, 3-methyl-5-ethylphenol, isopropylphenol, butylphenol, nonylphenol and dodecylphenol, and also halophenols, such as monochlorophenols, e.g. B. 2-chlorophenol, 3-chlorophenol, 4-chlorophenol and 3-methyl-4-chlorophenol, or dichlorophenols, e.g. B. 2,4-dichlorophenol, 2,5-dichlorophenol, 3,4-dichlorophenol and 2,6-dichlorophenol, also phenylphenols such as 2-hydroxydiphenyl, 4-hydroxydiphenyl, 2,2 · -dihydroxydiphenyl and 4,4'- Dihydroxydiphenyl, and also hydroxydiphenylmethanes, such as 2-hydroxydiphenylmethane or 4-hydroxydiphenylmethane, and C-phenylethylphenol or 2,2- (4 »4 '-dihydroxydiphenyl) propane.

30-40% solutions are generally used as aqueous formaldehyde solutions.

The molar ratio in which phenols and formaldehyde solutions are used is about 1 r 1 if you use the water distilled off from the reaction mixture in vacuo below 80 ° C, and 1: 1 * 2-1.4 »if you use the phenol half-formals separated as an organic phase.

The phenol half-formals produced according to the invention are distinguished by a very good microbiocidal activity. Further Because of their reactivity, they are valuable intermediates for the production of phenol-formaldehyde condensation products.

With the aid of the process according to the invention it is possible to produce pure semi-formals of phenols in a simple and excellent manner

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ORIGINAL iffvfSPECTED =.

Yields to manufacture «£,> / \ / ^ f $ 4 TTs? * "

According to the German Alleges chrift 1 241 432 are for the Production of pure semi-foxmales from phenols pure, anhydrous formaldehyde and catalysts such as acids, phosphines, Stibines, or nitrogen compounds, are required. It was therefore not foreseen that the reaction of phenols with aqueous formaldehyde solutions in the absence of catalysts according to the present invention also to pure phenol semi-formals would lead. It is also noteworthy that the process products are free from methylol compounds and their condensation products, which are acidic when aqueous formaldehyde solutions act on phenols in the presence or basic compounds easily form.

The parts given in the following examples are parts by weight.

example 1

108 parts of crude cresol are mixed with 100 parts of 30% formaldehyde solution Stirred at 50 ° C. for 1 hour. The water is then distilled off in a vacuum of 15-20 Torr at temperatures below 60 ° C

fin ⁰ 138 parts of semi- ^{formal cresol are obtained (nj u} : 1 _t 516O).

Example 2

94 parts of phenol are mixed with 100 parts of 30 # formaldehyde solution Stirred at 40 ° C. for 1 hour. The water is distilled off at 40-50 ° C. in vacuo. 124 parts of phenol are obtained.

Semi- ^{formal (nj u} : 1.5160).

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ORIGINAL INSPECTED

Example ⁸ 3 .

170 parts of 2-hydroxydiphenyl are mixed with 100 parts of 30 jug The formaldehyde solution is stirred for 1 hour at 50 - 55 ° C. In the At the same temperature, the water is distilled off in vacuo.

200 parts of 2-hydroxydiphenyl semi-formal are obtained (FP 49 - 51 ° C, n ^ °: 1.5936).

Example 4 .

198 parts of C-phenylethyl-phenol are mixed with at 55 - 60 ° C Stirring 75 parts of 40 # formaldehyde solution for 1 hour.

The water is then distilled off in vacuo. Man receives 228 parts of dC-phenylethyl-phenol semi-formal.

Example 5

128.5 parts of 4-chlorophenol are 40% with 75 parts Formaldehyde solution heated. Solution occurs at 40 ° C.

The mixture is kept at 40-50 ° C. for 1 hour and then the water is distilled off in vacuo: 170 parts of 4-chlorophenol semi-formal Cn ^ ⁰ : 1.5310) are obtained.

Example 6 ■

170 parts of 2-hydroxydiphenyl are mixed with 100 parts of 40 # The formaldehyde solution is stirred for 1 hour at 55 - 60 ° C. The reaction mixture is then left there for 2 hours Temperature settle and then separates the lower> organic phase. After brief drying in vacuo at 50-60 ° C., one obtains 200 parts of 2-hydroxydiphenyl semi-formal (FP 49 - 51 ° C, n | °°: 1.5936). -

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BATH

Claims (5)

Patent claims 1) Process for the production of Pheriol-Haiia'fo'rmaieri from Phenols and formaldehyde, thereby markedV - '"däÜ" man' Mixtures of phenols and aqueous formaldehyde solutions heated with stirring to a maximum of 80 ° C and then the phenol semi-formals formed are isolated. = 2) Method according to claim 1, characterized in that the phenol used is 2-hydroxydlphenyl. 3) Method according to claim 1, characterized in that the phenol used is oC-phenylethyl-phenol. 4) 2-hydroxydiphenyl semi-formal - ' 5) dC-phenylethyl-phenoi-half formal Le A 11 056 10 90 2 ^^^ 121 ORIGINAL