DE227659C - - Google Patents

Description

IMPERIAL

* (Ejcmpfar

PATENT OFFICE.

PATENT LETTERING

- JVl 227659 -. CLASS Mq. GROUP

Patented in the German Empire on December 25, 1908.

The methods of preparation of the nitrosoarylhydroxylamines known up to now are as follows :

1. Preparation from aryl hydroxylamines in acidic solution with sodium nitrite (E. Bamberger, Berl. Ber. 27 [1894] p. 1553; 31 [1898]

p. 574);

2. Representation from nitro bodies and hydroxylamine in the presence of sodium alcoholate (Angeli, Berl. Ber. 29 [1896] p. 1885; Meisenheimer and Patzig, Berl. Ber. 39 [1906]

p. 2534);

3. Preparation of nitrosophenylhydroxylamine from nitrosobenzene and nitrohydroxylamic acid (Angeli, Aiii R. Accad. Dei Lincei Roma [5] 9th II. [1900] pp. 44 to 46);

4. Presentation of nitrosophenylhydroxylamine from bromobenzene, magnesium powder and nitrogen oxide, NO (Sand and Singer, Ann. 329 [1903] pp. 190 to 194).

You can get through all of the presentation methods and forms of formation mentioned here to the free acids or to addition compounds of the nitrosoarylhydroxylamines which the latter can only be obtained by acidification with dilute mineral acids. The free nitrosoarylhydroxylamines are, however, very unstable and in some cases also explosive Connections, which is why their representation on a large scale is excluded.

The salts of the nitrosoarylhydroxylamines, on the other hand, are extremely stable.

A simple way has now been found to directly use salts of the nitroso arylhydroxy I-amines to represent

40

The method consists in the action of alkyl nitrites on aryl hydroxylamines im status nascens in alkaline or ammoniacal solution.

Example I.

30 g of nitrobenzene, about 200 ecm of water, about 100 ecm of concentrated ammonia solution and 35 g of amyl nitrite are vigorously stirred in a vessel, followed by 40 g of zinc dust entered quickly in small portions until all the nitrobenzene has disappeared. The reaction mixture, which has become very hot as a result of self-heating, is now filtered, the residue washed out with hot water and the filtrate, after taking off of the amyl alcohol, left to crystallize. The ammonium salt of nitrosophenylhydroxylamine then crystallizes in magnificent, snow-white crystals. Quantitative yield.

Example II.

100 g of aniline are quickly stirred into 1500 ecm of ice-cold, neutral sulfomonoperic acid solution (417 ecm - ■ ι atom 0), into which 130 g of amyl nitrite has previously been added (cf. Ber. 32 [1899] p. 1675/76). The simultaneous, gradual addition of dilute soda solution makes the whole thing slightly alkaline.

After a short time, all aniline is quantitatively converted into nitrosophenylhydroxylamine. The amyl alcohol is lifted off

and the nitrosophenylhydroxylamine formed is quantitatively precipitated as the copper salt.

By reducing the nitro or oxidation of the amino group in the presence of amyl nitrite the following nitrosoarylhydroxylamines have been isolated so far:

^N0

NO

^no

NH-COCH.

OCH ^

-N

/ ■

NO

OK OCH ₉

, NO OK

OH

_{m /} N 0 ^{N <} 0H «ο

^N0

CHO

CHO

NO OH

COH

r / -

■ NO

./NO

, NO ^S OH -COOH

N (CH ₃ J ₂

The properties of some nitrosoarylhydroxylamines prepared by the present process and their salts are given below.

The nitrosophenylhydroxylamine ammonium salt is easily soluble in hot alcohol and crystallizes out again in broad silver-white flakes. F. P. 163 to 164 ° (bath 155 °). It sublimes on the water bath between watch glasses.

The sodium or potassium salt crystallizes in snow-white needles from alcohol.

Both the ammonium salt and the alkali salts give all typical reactions of nitrosophenylhydroxylamine, namely:

Nitrosobenzene when heated with acids, reduction to diazo compounds when standing with diluted acids at room temperature. Forms with ferric chloride and a mineral acid from the alkali (ammonium) salt immediately the red, ether-soluble iron salt.

The nitrosophenylhydroxylamine iron

forms garnet-red needles from ether, united to form rosettes, with a blue metallic surface shimmer. Resistant to diluted acids at room temperature; the ER ₁₁₅ warm Nitrosobenzolbildung. Soluble in concentrated hydrochloric acid with a deep red color. Immediately broken down into iron hydroxide and nitrosophenylhydroxylamine sodium with caustic soda:

/ NO
^{6 5} ^ 0Na

The iron salt is easily soluble in ether, benzene. Chloroform, nitrobenzene and others organic solvents, insoluble in water and in ammonia.

The nitrosophenylhydroxylamine copper crystallizes from ammonia in beautiful, blackish-gray crystals. Insoluble in water, fairly easily soluble in ether, chloroform and nitrobenzene.

ίο From ammonia or alkali it is immediately broken down into copper hydroxide and the corresponding one Nitrosophenylhydroxylamine salt.

α-nitrosonaphthylhydroxylamine ammonium.

Snow-white leaves that soon turn pink in daylight and are rather fickle are. Fairly soluble in cold water; this solution is also colored pink in daylight. Boiling Water decomposes the ammonium salt with the formation of a-nitrosonaphthalene (pungent Odor).

₂ . α- nitrosonaphtylhydroxylamine sodium
(Potassium).

White crystals, very much in cold water easily soluble. . Both the alkali salts and the ammonium salt give those listed above typical reactions of 'nitrosoarylhydroxylamines.

α-nitrosonaphthyl hydroxylamine copper.

Gray-blue, 'shiny needles, insoluble in Water.

Analysis:

Substance = 0.1213 g,

CO ₂ = 0.2447 g.

H ₂ O = 0.0371 g,

C = 55.0 percent,

H = 3.4 percent.

Theoretically for (C ₁₀ H ₁ N ₂ O ₂ ) 2 Cu :
⁴ ^ C = 54.9 percent,

H = 3.2 percent.

The new process makes it possible to produce any aromatic nitro or amino group by the nitrosoaryl hydroxylamine group

or also

-N = N-OH

to replace what was not possible before, as in many cases it was achieved by reducing the Nitro or by oxidation of the amino group does not succeed, the intermediate phase:

to grasp or isolate.

Even according to Angeli's method (Berl. Ber. 29 [1896] p. 1884, Rend. Lincei 8, 28) it is not always possible to convert aromatic nitro bodies into nitrosoarylhydroxylamines. Angeli always received 4-nitro-i-aminonaphthalene from a- nitronaphthalene, which, however, is not formed from the intermediate phase a-nitronaphtylhydroxylamine, as he thinks it is probable, but is most likely formed directly by replacing a hydrogen atom with hydroxylamine by NH (Chem. Centralbl 1899, II, p. 371; BerL Ber. 39 [1906] p. 2533.

The use of the nitrosoarylhydroxylamines for the dye representation results initially without further ado that one can easily nitroso or nitrosoarylhydroxylamines Can produce diazo bodies (Berl. Ber. 27 [1894] p. 1553; 28 [1895] p. 246, 248; 31 [1898] P. 575; 36 [1903] p. 1615).

In addition, however, the nitrosoarylhydroxylamines are also used for the preparation of stain dyes of utmost importance as they form a salt and one for the creation of coordinative bonds with a metal atom capable group contained in such a position that an inner metal complex salt can arise. Now it is known to depend on Werner's latest theory (Berl. Ber. 41 [1908] p. 1062) the ability to to draw chemical compounds on pickling from their property of being inner metal complex salts to build. The use of the nitrosoarylhydroxylamines, which can now be produced cheaply by the present process, is used for The representation of chemically pure metals or metal salts results from the following:

Example 1.

A solution that z. B. In addition to iron and copper salts, other metal salts (e.g. of nickel or cobalt), gives in dilute acids, with an aqueous solution of nitrosophenyl - (naphtyl) - hydroxylamine sodium (-potassium, -ammonium) added, a quantitative precipitation of iron and copper in the form of the "inner complexes." Salts «. All other metals that can be used as companions to iron and copper, remain dissolved in the acid because they do not contain nitrosophenyl - (naphtyl) - hydroxylamine enter into such compounds which are insoluble in water and dilute acids. The precipitated Copper and iron complex salts fil-. trotted. man off, washes the remaining

adhering acid and separates these "salts" with concentrated ammonia.

Nitrosophenylhydroxylamine iron remains undecomposed on the filter; is in the filtrate all copper is in the form of the complex copper ammonia salt. By boiling the Ammonia or acidification gives nitrosophenylhydroxylamine copper. As well as the inner complex iron as well as that

ίο Copper salt decomposes immediately with alkali in iron (copper) hydroxide and the corresponding alkali salt of nitrosophenylhydroxylamine, which is now going back into operation.

If you take nitrosonaphtylhydroxylamine potassium (-sodium, -ammonium), so is that Process even easier as the nitrosonaphtylhydroxylamine iron is instantly mixed with ammonia Iron hydroxide and nitrosonaphtylhydroxylamine ammonium is decomposed. You can through it the excreted internal complex copper and iron salts right on the filter with ammonia into chemically pure iron hydroxide and complex copper ammonium salt decompose which latter is in the filtrate. The copper is now extracted from the salt exactly as indicated in the nitrosophenylhydroxylamine experiment.

Example 2.

If you z. B. unlocks a nickel stone, dissolves in technical hydrochloric acid and the hydrochloric acid solution diluted with water with that of nitrosophenyl (naphthyl) hydroxylamine potassium (-sodium, -ammonium) is added, copper and iron are precipitated, while nickel remains in solution. Man filtered, washed with water and, as indicated above, decomposed the precipitate, as the case may be nitrosophenyl- or nitrosonaphtylhydroxylamine has been used for precipitation, with alkali or with ammonia. In this way chemically pure iron and copper hydroxide are obtained. From the first Mother liquor, however, can be electrolytically deposited nickel. ■ ■ ■

Chemically pure iron or copper can also be obtained by burning the inner ones complex iron or copper salts obtained by themselves or in a hydrogen stream.

The ability of nitrosoarylhydroxylamines to form internal metal complex salts with certain metals is affected by nuclear substitution. While nitrosophenyl (naphtyl) hydroxylamine forms such "salts" only with iron or copper. B. this rare property in o-Aldehydonitrosophenylhydroxylamin extended to nickel and lead.

Claims (1)

Patent claim: Process for the preparation of the alkali and ammonium salts of nitrosoarylhydroxylamines, -consisting of either aromatic nitro compounds in the presence of alkyl nitrous acid esters reduced in alkaline or ammoniacal solution with zinc dust or aromatic amino compounds in the presence of alkali, alkali carbonates or ammonia with nitrous acid alkyl esters and sulfomonoperacid treated.