DE139989C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

In the patent specification 125699 has been described that the substitution products of o-o ^ dinitrodiphenyls

in a similar way to the derivatives of nitrodiphenylamine

NH

are particularly suitable for the representation of sulfur dyes. It has now been found that another number of valuable raw materials for sulfur paints by the Derivatives of Mononitrodiphenylinetbans and Dinitrodiphenylmethans from the formulas:

TVO ₉

and

is formed. The dyes obtained here are exactly the same if you think of one singly or by a diphenylmethane nitrated twice in the ortho position to the methylene group goes out. If symmetrically substituted diphenylmethanes are used for the nitration, it should be advisable to to introduce two nitro groups, since then the nitration proceeds more smoothly, while with unsymmetrically substituted derivatives, the introduction of a nitro group is sufficient. Naturally a mixture of mono- and dinitro compounds can also be used.

The simplest representatives of orthonitrated diphenylmethanes have been described so far the o-o ^ dinitro-p-p'-diamidodiphenylmethane (Gram, Ber. 25, p. 304) from p-diamidodiphenylmethane and the o-o ^ dinitro-p-p -'-tetramethyldiamidodiphenylmethane (Pinnow, Ber. 27, p. 3163) from the tetramethylated diamidodiphenylmethane, both by adding two molecules of potassium nitrate, or the equivalent amount of nitric sulfuric acid in receive the sulfuric acid solution of the base. One tries by applying only to represent the corresponding mononitro compounds to a molecule of potassium nitrate you always have a lot of dinitro compound in addition to the unchanged base. On the other hand, it succeeds To take mononitro compound, if one with a large excess of base, for example two molecules of base on one molecule of saltpetre, works. Then there is only a mixture of unchanged and of mononitrated base, which are obtained by fractional precipitation

let the sulfuric acid solution separate with soda.

The ο - nitro - ρ - ρ '- diamidodiphenylmethane crystallizes from alcohol in atlas-glossy, sulfur-yellow needles, which melt ^{at ioobis ιοί 0.}

Calculated for C ₁₃ H ₁₃ O ₂ N ₃ : found:

C 64.20 percent, C 64.73 percent,
H 5.35 - H 5.49

JV. 17.28 -. JV 17.41

The o-nitro p-p'-tetramethyldiamidodiphenylmethane Crystallizes from alcohol in groups of red, pyramidal crystals with a melting point 96 to 96.5 °.

Calculated for C ₁₁ H ₂₁ O ₂ N ₃ : found:

C 68.23 percent, C 67.79 percent,
H 7.02 - H 7, u

JV 14.04 -. JV 14.38

Example I. When heating 1 part Dinitrodiamidodiphenylmethan gradually with 2 parts of sulfur and 5 parts of sodium sulphide, the melt at 150 to 170 ⁰ is water soluble and contains then a greenish black, dye nouns, but that is not acid resistant. By further increasing the temperature up to 240 to 250 ⁰ , the dye changes into a dark brown, extremely genuine cotton dye. Exactly the same dye is obtained by heating 1 part Mononitrodiamidodiphenylmethan with 2 parts of sulfur, and 4 parts of sodium sulphide at 240 to 250 ^0th

The powdered melt can be used directly for coloring. It dissolves in Water with a reddish black color, which by adding caustic soda or sodium sulphide is not changed. Hydrochloric acid falls brown-black, insoluble in sulfuric acid Flakes off. On cotton, the dye pulls out of cold or hot, saline Soak up with a dark brown. Subsequent chrome plating gives the nuance unaffected. The color remains unchanged even when the fibers are placed in sodium hydroxide solution or concentrated hydrochloric acid.

Example II. If ι part of mononitrotetramethyldiamidodiphenylmethane is heated in the same way with 2 parts of sulfur and 4 parts of sodium sulfur or 1 part of dinitrotetramethyldiamidodiphenylmethane with 2 parts of sulfur and 5 parts of sodium sulfur to 260 to 280 ⁰ , a dye which is soluble in water and has a reddish brown color is obtained. which dyes cotton with a pure and very real yellow-brown. The dye shows the same behavior towards reagents as the dye from nitrodiamidodiphenylmethane.

Example III. More highly nitrated derivatives of tetramethyldiamidodiphenylmethane can also be used. If you z. B. to the nitration mixture obtained by adding two molecules of potassium nitrate to the sulfuric acid solution of tetramethyldiamidodiphenylmethane, after standing for about twelve hours, ^{gradually adding another amount of saltpetre corresponding to two molecules at 10 to 15 0} , a nitro body is formed which when the sulfuric acid solution is poured in no longer remains in solution in water, but separates out completely as an orange precipitate. The body can be fused directly after washing out and, with two parts of sulfur and six parts of sodium sulphide at 260 to 280 °, produces a brown dye of a darker shade than the brown of the dinitro compound. The yellow-brown color of the aqueous solution is not changed by adding caustic soda or sodium sulphide. Hydrochloric acid precipitates brown flakes, which are insoluble in sulfuric acid.

Other dyes of a similar type can be obtained by using the tetraethyldiamidodiphenylmethane goes out. That represented by nitrating the sulfuric acid solution Dinitrotetraäthyldiamidodiphenylmethan crystallizes from alcohol in yellow-red, under lamellar striped leaves under the microscope, which melt at 121 to 121.5 °.

Claims (1)

Patent claim: Process for the representation of nouns dyes by heating p-p ^ amido derivatives or of alkylated p-p'-amido derivatives of o-mononitrodiphenylmethane or of the o-o'-dinitrodiphenylmethane or the polynitro body derived from the latter with Sulfur and alkali sulfur.