DE180204C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

PATENT LETTERING

- JV! 180204 - CLASS 12 ο. GROUP

BADISCHE ANILINE AND SODA FACTORY in LUDWIGSHAFEN a. Rh.

aromatic amines.

Patented in the German Empire on July 23, 1905.

Under the. halogenate aromatic amines take studies made according to those three and more halogenated anilines, which have two halogen atoms in ο-position to the amino group contain a special place. So they put z. B. already the occurrence of a Alkyls or an acyl in the amino group oppose considerable resistance. It ίο this does not seem particularly surprising, given the presence of the atomic group

St.

NH ₂

St.

so-called steric hindrances in the reactivity of the amino groups easily are understandable.

These relationships may be illustrated by a few examples:

While it is known that the 2 ^ -dias chloraniline, which contains halogen only in one ortho position, contains 90 percent formic acid in slight excess (1 mol.: 1 × 6 Mol.) By heating for 1 hour on a water bath into the formyl compound can be transformed (cf. Ber. XXXII, p. 3636), one arrives at that of 2: 4: 6- trichloroaniline, in which both o-positions are occupied by halogen, only through Treat the same with excess anhydrous formic acid at the boiling point for 60 to 70 hours (cf. Ber. XXXII, p. 3636); remains as was found, even when using 6.4 mol. of anhydrous formic acid, a considerable part of the base unchanged. The as.-trichloroaniline and ν-tetrachloroaniline, in each of which only contains an o-position chlorine, with 90 percent formic acid the pure formyl compound is heated in a slight excess in excellent yield, while from the corresponding anilines, which are halogen-substituted in both ο positions, the s-trichloroaniline and the as.-tetrachloroaniline no trace of the corresponding formyl compounds is obtained under the same conditions.

The situation is similar for the acetyl and benzoyl compounds. Acetylation With the help of acetyl chloride, the chloroanilines with only one chlorine atom in the o-position occur: 2 · 5 - dichloroaniline (p-di- chloraniline) and as. Trichloroaniline so easily that the reaction can be prevented by diluting with Glacial acetic acid still has to be softened (Ann. 196, 215). In contrast, the doubly orthochlorous are substituted Compounds, the s-trichloroaniline (cf. also Ber. 32, 3636) and the as-tetrachloroaniline can only be acetylated with difficulty; the temperature of these bodies must even be substantial when acetyl chloride is used.

Hch above its boiling point (56 ° C), namely to 100 to 125 ⁰ (in the tube). From benzoyl compounds of multiple chlorinated bases, obtained by benzoylation of the

, 5 base, is known only to that of s-trichlojaniline. They are obtained according to Chattaway, Orton and Hurtley (Ber. 32, p. 3637) by heating the s-trichloroaniline with ¹ benzoyl chloride on a water bath. From the information provided by the same authors elsewhere (Ber. 33, p. 2396) it can be seen that the reactivity of s-trichloroaniline towards benzoyl chloride is extremely reduced compared to that of o-chloroaniline. The latter can namely be converted into the benzoyl compound by the action of benzoyl chloride on the ο-chloroaniline distributed in cold alkaline water according to the cited literature reference by the Schotten-Baumann method. An aniline with only one chlorine in the ortho position thus proves to be much more reactive with benzoyl chloride than the s-trichloroaniline with two chlorine atoms in the position ortho to the amino group. . "'......

Since the entry of alkyl into aromatic bases, the basic properties the body in question is known to be pushed down even further and thus the Entry of an acyl. Another complication was that it was impossible to foresee whether the production would be carried out of alkyl acyl compounds of the polychloroanilines mentioned from their alkyl compounds would work at all.

It has now been shown that one is able to remove organic acid residues, although not by means of the acids themselves, but surprisingly smooth by means of their chlorides and anhydrides to introduce into the alkyl compounds of the above polychloroanilines, so that one leads to the first representatives of alkylated acyl compounds with higher chlorinated bases arrives.

Example I.

100 parts by weight of s-monomethyltrichloroaniline (m.p. 28 to 20, ⁹ C.) are heated under pressure with 100 parts by weight of glacial acetic acid and 20 parts by weight of acetyl chloride in a water bath until a sample shows no further progress of the reaction. After blowing out the hydrochloric acid, any acetyl chloride and glacial acetic acid still present are distilled off and the residue is crystallized from a suitable solvent, e.g. B. diluted alcohol cleaned. Is obtained as the s-Methylacetyltrichloranilid of mp. 89-90 ^0th

Is used in place of the s-Monomethyltrichloranilins the equivalent amount of Monoäthyltrichloranilins (Sp. 148-153 ⁰ C. at 25 mm pressure) or the s-Monobenzyltrichloranilins (Sp. 225-227 ⁰ C. at 21 mm pressure), one obtains the s-Äthylacetyltrichloranilin from melting point 50 to 51 ° respectively. the s-benzylacetyltrichloroaniline with a melting point of 61 °.

If the appropriate amounts of the alkyl compounds of the as-tetrachloroaniline are used, thus one obtains: here too the acetal compounds of these bases.

Example IL

Acetylation using acetic anhydride is technically easier and smoother. '

100 parts by weight of s-monoäthyltrichloranilin (liquid Sp. 148 to 153 ⁰ at 25 mm pressure), 35 parts by weight of glacial acetic acid and 65 parts by weight of acetic anhydride are heated on the reflux condenser for 6 to 8 hours, respectively. until a sample shows the completion of the reaction (absence of secondary base). The acetic acid is then distilled off and the residue is recrystallized.

In the same way, the acetyl derivatives of s - monomethyltrichloroaniline and des s-monobenzyltrichloroaniline and the alkyl compounds des as. tetrachloroaniline and pentachloroaniline. received.

Example III.

100 parts by weight of s-monoethyl trichloroaniline are mixed with 50 parts by weight of benzoyl chloride; strong warming occurs. To complete the reaction is heated for ι hour in an oil bath of 150 ^0; When it cools, the mass solidifies to form a crystal cake. The recrystallized from alcohol's Äthylbenzoyltrichloranilid melts at 127-128 ^0th

The bases used as starting material can be obtained by chlorinating the chlorohydrates of the alkyl compounds of lower chlorinated anilines, namely:

1. the alkyl products of s-trichloroaniline from the corresponding alkyl products of Aniline, .110

2. the alkyl products of as-tetrachloroaniline from the corresponding alkyl products such lower chlorinated anilines, which have a chlorine atom meta to the amino group contain, .

3. the alkyl products of pentachloroaniline from the corresponding alkyl products of such lower chlorinated anilines, which have two chlorine atoms meta to the amino group contain. .

The products obtainable by the present process are intended primarily as

Find camphor substitutes in the manufacture of celluloid-like bodies use.

Claims (1)

Patent claim: Process for the preparation of alkyl acyl compounds triple and multiple chlorinated aromatic amines with two chlorine atoms ortho to the amino group, characterized in that one the alkyl compounds of the amines mentioned with acid chlorides or acid anhydrides treated.