DE3932352A1 - N-glycidyl-aniline cpds. prepn. - by reacting aniline cpd. with epichlorohydrin in absence of oxygen, then de:hydrochlorinating at low temp. - Google Patents

Abstract

Substd. (sic) N-glycidylaniline cpds. (I) are prepd. by (1) reacting (opt.) substd. aniline cpd. (II) with epichlorohydrin (III) in protonic solvent and with exclusion of O2 (2) dehydrochlorinating chlorohydrin so obtd. with aq. soln. of base at -10 to 0 deg.C. USE/ADVANTAGE - As monomer, comonomer, or modifying agent in polymer reactions, esp. in temp.-resistant epoxide resin systems, esp. encapsulation compsns. for microelectronic components, adhesives, reinforced epoxide resin materials, components of photopolymerisable information-recording materials. Method is simple, (I) are obtd. relatively pure.

Description

Substituted glycidylanilines are component temperature Resistant epoxy resin systems and find application as a cladding masses for microelectronic components, as adhesives, as a base material for reinforced epoxy resin materials and as a system component of photopolymerizable information recording materials.

It is known that substituted glycidylanilines of formula V or VI

from the analogous aniline derivative, cf. Formula I or II,  

by reaction with epichlorohydrin at elevated temperature can be obtained. The synthesis is in aromatic Solvents, such as. As toluene performed. The required dehydrohalogenation also occurs at higher temperatures (Polym. Bull. 14 (1985) 123). Other authors use aniline derivatives with epichlorohydrin Ethanol-water mixtures to chlorohydrins according to formula III or IV around.  

This reaction takes place at the boiling point of the solvent. Dehydrohalogenation also takes place here at temperatures of 50-80 ° C (EP 2 39 804, EP 00 90 681). Furthermore, it is known that in the dehydrohalogenation kata lysatoren can be used, wherein z. B. quaternary Ammonium salts are used (EP 01 43 075, EP 00 76 584, Journal of Applied Polymer Science 30 (1985) 2907). The on glycidylanilines obtained in this way are in higher Aus booty and better quality than connections, which were prepared without a catalyst (EP 01 43 075).

Other authors synthesized substituted glycidylanilines, by adding an aniline derivative with epichlorohydrin in the presence of a catalyst at 70 ° C for 24 h and the dehydroha leaching with caustic soda also in the presence of a Catalyst at temperatures of 10-15 ° C perform (EP 76 584). Furthermore, it is described in the literature that aniline derivatives with epichlorohydrin in water-alcohol mixtures in the boiling point be implemented heat of the solvent. The dehydrohalogens  Nitrium hydroxide is applied at approx. 10 ° C or room temperature in substance. The synthesis methods mentioned here have the following disadvantages:

• - When using primary aromatic anilines is a certain proportion of monoglycidyl compounds in the reaction product available. The presence of monoglycidyl compounds leads to discoloration of the product in case of longer storage time. In addition, the storage time in the presence of such Verbin relatively short. Monoglycidyl compounds are in particular then in the reaction product when the reaction is in toluene is carried out.
• - Other by-products formed at higher temperatures are derivatives of tetrahydroquinoline. These substances also contribute to the fact that the end product is highly colored and has short storage times.
• At higher temperatures, higher molecular weight, formed oligomeric compounds. The presence of oligomers results in a higher viscosity and a smaller one Storage stability of the final product.
• - When working in the presence of a catalyst, must this after completion of the reaction almost quantitatively ent be removed, since already traces of this the storage time of the End product can worsen. Also other side reactions can be accelerated by traces of catalyst.
• - The presence of atmospheric oxygen results in higher temperature to oxidation of the aniline derivatives, what with a intense discoloration of the reaction mixture is connected.

The aim of the invention is to substituted glycidylanilines simple way to produce in relatively high purity.

The invention is based on the object, a simple Ver for the preparation of substituted glycidylanilines in to develop relatively high purity. According to the invention Problem solved that substituted anilines under Exclusion of oxygen can be converted to chlorohydrins and these  then dehydrohalogenated in the temperature range of -10-0 ° C. become. In this case, substituted anilines of the formula I.

wherein the aromatic any substituents R₁, R₂, R₃, R₄ contain can, but preferably R₂, R₃, R₄ can mean: H, alkyl with 1-6 C atoms, aralkyl with 1-6 C atoms in the ali phatic part, ester groups, these being preferably from aliphatic radicals with 1-6 C atoms or from phenolic Esters derived, alkoxy with 1-6 C-atoms, phenoxy, others primary, secondary or tertiary amino groups, where R₁ is H, alkyl having 1-6 C atoms, aralkyl having 1-6 C atoms in the aliphatic part can mean reacted with epichlorohydrin, in a protic solvent in the absence of air at slightly elevated temperature in one Interval of 35-50 ° C, to compounds of formula III

wherein R₁, R₂, R₃, R₄ have the same meaning as in formula I. and these to the corresponding glycidyl compounds of Formula V in ice cold in the temperature range of -10-0 ° C with the dehydrohalogenated aqueous solution of a base,  

wherein R₁, R₂, R₃, R₄ have the same meaning as in formula I. and by this method all amine hydrogens of aniline derivative I by glycidyl groups corresponding to formula V sub be stituiert. Furthermore, substituted anilines of Formula II

wherein the substituents R₁, R₂, R₃, R₄, R₅ are included, R₂, R₃, R₄, however, have the same meaning as in formula I. and R₅ may have the same meaning as R₂, R₃ or R₄, wherein R₁ is H, alkyl having 1-6 C atoms, aryl or aralkyl with 1-6 C atoms in the aliphatic part can mean where X is a covalent bond, an alkylene group having 1-6 C atoms, a Alkylenarylenalkylengruppierung with 1-6 C-atoms in the aliphatic part, an arylene moiety, a heteroatom such as O, SO₂ can mean reacted with epichlorohydrin, in a protic solvent with exclusion of air at slightly elevated temperature of 35-50 ° C, to compounds of formula IV,  

X, R₁, R₂, R₃, R₄, R₅ have the same meaning as in Formula II and these to the corresponding glycidyl compounds of formula VI in ice cold at temperatures of -10-0 ° C with the dehydrohalogenated aqueous solution of a base,

wherein X, R₁, R₂, R₃, R₄, R₅ have the same meaning as in formula II. According to the invention in the synthesis all Amine hydrogens substituted by glycidyl groups and the obtained epoxides of formula V or VI are in sufficient Purity for further use.

From EP 01 43 075 it is known that substituted glycidylanilines can be synthesized by substituted aniline derivatives of the formula II in the presence of a catalyst salt be reacted with epichlorohydrin at 60-90 ° C and then at 70 ° C, the dehydrohalogenation with sodium hydroxide solution he follows. Surprisingly, it has been found that the reaction of Epichlorohydrin with aromatic amines according to formula I or II to the compounds of formula III or IV under inert gas in  a protic solvent at temperatures of 35-50 ° C. runs almost quantitatively and thus the proportion of monoglycidyl compounds is very small and that the dehydrohalogenation with caustic soda in ice-cold without substantial formation of By-products expires. The desired glycidyl compounds of Formula V or VI are already available as crude for many users clean enough. Due to the mild reaction conditions the formation of oligomeric impurities becomes apparent pushed back, since this process is known to be preferred higher temperatures expires. It has also been found that working under inert gas with contributes to the relaxing raw products in a Layer thickness of 2 mm are almost colorless. On a catalyst can be waived, since the reaction without this completely expires. Due to the phase separation in the dehydrohalogenation in the Cold remains numerous polar impurities in the aqueous phase. Through this effect, the purity of the desired glycidyl derivative according to formula V or VI in the increased organic phase. The epoxides of the formula V or VI thus obtained have against above those produced by conventional methods the advantage that the product is more pure and therefore the color brighter and the storage stability are greater. The product yield is higher in some cases as well was worked on gentler conditions. Epoxides which are produced by this process can without further purification for many polymer-specific Reactions are used immediately because their purity is sufficient is.

embodiments Example 1

In a 1 liter flask under inert gas (argon) 3.1 mol Epichlorohydrin at a temperature of 50 ° C to a mixture of 1.4 moles of aniline and 380 ml abs. Ethanol added dropwise. The mixture is added at the end of addition for 6 hours stirred at this temperature. Subsequently, the alcohol distilled off in a water jet pump vacuum at 40-50 ° C. The Residue is cooled to 0 ° C in an ice-salt bath. At this temperature 2.8 mol. Within one hour a 45% sodium hydroxide solution is added dropwise so that the temperature in the flask does not exceed 2 ° C. It will be 2 hours after touched. Subsequently, the reaction mixture in 500 ml Add water and several times with a 5% saline solution washed. After this process is distilled three more times Washed water and the organic phase over Dried sodium sulfate. A distillation in an oil pump vacuum gave 80% yield, which was colorless.

Boiling point in vacuo (0.5 torr): Kp _0.5 = 145 ° C
Epoxide content <99.5%
Chlorine content <0.2%

If, instead of inert gas under reduced pressure of p = 12 Torr, so also gives 80% yield of reaction product.

Epoxide content <99.5%
Chlorine content <0.2%

If instead of aniline p-toluidine is used, then the Yield of the product 85%.

Kp _0.5 = 165 ° C
Epoxide content <99.5%
Chlorine content <0.2%

If, instead of 1.4 mol of aniline, 2.8 mol of N-ethylaniline are used, so the corresponding product is obtained in 95% yield.

Epoxide content 99.5%
Chlorine content 0.2%

example 2

In a 1 liter flask, 380 ml of absolute ethanol and 0.7 mol 4,4'-Diaminodiphenylmethan submitted under inert gas atmosphere. During the reaction, an argon stream passes through the solution directed. The mixture is heated to 50 ° C and this 3.1 mol of epichlorohydrin are slowly added dropwise, so that the temperature does not exceed 50 ° C. It will still be Stirred for 6 hours at this temperature. Subsequently, will cooled to 0 ° C and within 2 hours 2.8 mol of a 45% sodium hydroxide solution was added dropwise so that the temperature 2 ° C in Piston does not exceed. It will be after the end of the addition Stirred for 2 hours at this temperature. There are two Phases, with the top, the organic, further worked up becomes. For this purpose, it is poured into 2 l of water. This mixture is shaken with toluene, three times with a 2.5% Washed brine and then with distil shaken out the lanced water until the aqueous phase free from Chloride ions is. The organic phase is washed with sodium sulfate dried and the excess toluene is in Rotationsver steamer deducted. A pale yellow, viscous oil is obtained with a yield of 90%.

C 70.5% (over 71.09%) H 7.1% (above 7.1%) N 6.43% (over 6.63%)

If instead of 4,4'-diaminodiphenylmethane 2,2 (4,4'-di Aminodiphenyl) -propane used so is a yield of Product of 80% received.  

If instead of 4,4'-diaminodiphenylmethane N, N-di-benzyl 4,4'-diaminodiphenylmethane used, so is a yield obtained at 80% product.

Claims (3)

1. A process for the preparation of substituted glycidyl anilines, from substituted anilines by reaction with epichlorohydrin in a protic solvent and subsequent dehydrohalogenation with the aqueous solution of a base, characterized in that substituted anilines are reacted under exclusion of oxygen to chlorohydrins and then in the temperature range of - Be halogenated 10 to 10 ° C dehydro. 2. The method according to claim 1, characterized in that substituted anilines of the formula I. wherein the aromatic may contain any substituents R₁, R₂, R₃, R₄ ent, but preferably R₂, R₃, R₄ may mean: H, alkyl having 1-6 C atoms, aralkyl having 1-6 C atoms in the aliphatic part, Ester groups, these preferably being derived from aliphatic radicals having 1-6 C atoms or from phenolic esters, alkoxy having 1-6 C atoms, phenoxy, further primary, secondary or tertiary amino groups, where R₁ is H, alkyl having 1-6 C atoms, aralkyl having 1-6 carbon atoms in the aliphatic part, reacted with epichlorohydrin, in a protic solvent with exclusion of air at slightly elevated temperature in a temperature range of 35-50 ° C, to compounds of formula III wherein R₁, R₂, R₃, R₄ have the same meaning as in formula I and these dehydrohalogenated to the corresponding glycidyl compounds of formula V in ice-cold in the temperature range of -10-0 ° C with the aqueous solution of a base, wherein R₁, R₂, R₃, R₄ have the same meaning as in formula I and according to this method all amine hydrogens of the aniline derivative I are substituted by glycidyl groups corresponding to formula V. 3. The method according to claim 1, characterized in that substituted anilines of the formula II wherein the substituents R₁, R₂, R₃, R₄, R₅ are included, R₂, R₃, R₄, however, have the same meaning as in formula I and R₅ may have the same meaning as R₂, R₃ or R₄, wherein R₁ is H, alkyl with 1 -6 C atoms, aryl or aralkyl having 1-6 C atoms in the aliphatic part, where X is a covalent bond, an alkylene group having 1-6 C atoms, a Alkylenarylenalkylengruppierung with 1-6 C atoms in the aliphatic part , an arylene group, a heteroatom such as O, SO₂ may mean, reacted with epichlorohydrin, in a protic solvent with exclusion of air at slightly elevated temperature of 35-50 ° C, to compounds of formula IV, X, R₁, R₂, R₃, R₄, R₅ have the same meaning as in formula II and these dehydrohalogenated to the corresponding glycidyl compounds of formula VI in ice-cold at temperatures of -10-0 ° C with the aqueous solution of a base, where X, R₁, R₂, R₃, R₄, R₅ have the same meaning as in formula II.