US2927136A - Stabilization of aromatic amines - Google Patents

Stabilization of aromatic amines Download PDF

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Publication number
US2927136A
US2927136A US605944A US60594456A US2927136A US 2927136 A US2927136 A US 2927136A US 605944 A US605944 A US 605944A US 60594456 A US60594456 A US 60594456A US 2927136 A US2927136 A US 2927136A
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Prior art keywords
chloroaniline
weight
aromatic amines
dibutyl tin
stabilization
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US605944A
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Leslie M Schenck
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GAF Chemicals Corp
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General Aniline and Film Corp
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Priority to US605944A priority Critical patent/US2927136A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/90—Stabilisation; Use of additives

Definitions

  • This invention relates to the stabilization of aromatic amines, and relates more particularly to the stabilization of aromtaic amines against discoloration by deterioration during storage.
  • Aromatic amines such as meta-chloroaniline, aniline, the toluidines and the like are normally colorless directly after preparation or distillation. However, the aromatic amines have a tendency to darken in color during storage, and this darkening is greatly accelerated when the storing is at an elevated temperature.
  • Another object of this invention is the provision of color-stable aromatic amines which are capable of being stored for an appreciable length of time without excessive discoloration.
  • aromatic amines which are normally colorless when prepared and have a tendency to darken in color during storage may have this tendency toward color deterioration retarded by adding thereto a small amount of stabilizing agent such as thiourea or an alkyl tin compound. While alkyl borates may also be employed as stabilizers for the aromatic amines, they are not as efiective as the thioureas or the alkyl tin compounds.
  • a stabilizer such as ethylene thiourea, dibutyl tin oxide, dibutyl tin dilaurate, triethyl borate, tributyl borate to the aromatic amine the tendency toward color deterioration thereof during storage is substantially retarded.
  • a stabilizer such as ethylene thiourea, dibutyl tin oxide, dibutyl tin dilaurate, triethyl borate, tributyl borate
  • this invention is applicable to any aromatic amine having a tendency to darken during storage such as, for example, aniline, alkyl anilines, halogen substituted anilines, toluidines and naphthylamines, it is particularly applicable in connection with the color stabilizing of m-chloroaniline.
  • EXAMPLE To portions of freshly distilled m-chloroaniline is added one of the stabilizing compounds, ethylenethiourea, dibutyl tin oxide, dibutyl tin laurate, triethyl borate and tributyl borate, in an amount of 0.1% by weight on the "ice Storage tests on m-chloroaniline Optical Density after storage at186 r2 Stabilizer, 0.1% Concentration 0 hours 96 hours 288 hours ntrol 3 98 Ethylene Thlonrea.
  • the stabilizing compounds ethylenethiourea, dibutyl tin oxide, dibutyl tin laurate, triethyl borate and tributyl borate
  • Process for retarding the color deterioration of m-chloroaniline which comprises adding to the m-chloroaniline 0.1% by weight, on the weight of the m-chloroaniline, of dibutyl tin oxide as the sole stabilizing agent.
  • Process for retarding the color deterioration of m-chloroaniline which comprises adding to the m-chloroaniline 0.1% by weight, on the weightof the m-chloroaniline, of dibutyl tin dilaurate as the sole stabilizing agent.
  • a color stable m-chloroaniline consisting essentially of m-chloroaniline having incorporated therein 0.1%
  • a color stable m-chloroaniline consisting essentially of m-chloroaniline having incorporated therein 0.1% by weight, on the weight of the m-chloroaniline, of dibutyl tin dilaurate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Detergent Compositions (AREA)

Description

United States Patent 2,927,136 STABILIZATION ()F AROMATK. AIVEINES Leslie M. Schenck, Westfieid, NJ., assignor to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Application August 24, 1956 Serial No. 605,944
4 Claims. (Cl. 260578) This invention relates to the stabilization of aromatic amines, and relates more particularly to the stabilization of aromtaic amines against discoloration by deterioration during storage.
Aromatic amines such as meta-chloroaniline, aniline, the toluidines and the like are normally colorless directly after preparation or distillation. However, the aromatic amines have a tendency to darken in color during storage, and this darkening is greatly accelerated when the storing is at an elevated temperature.
It is an important object of this invention to provide a process for effectively retarding the discoloration of aromatic amines during storage.
Another object of this invention is the provision of color-stable aromatic amines which are capable of being stored for an appreciable length of time without excessive discoloration.
Other objects and advantages of this invention will appear from the following description and claims.
I have found that aromatic amines which are normally colorless when prepared and have a tendency to darken in color during storage may have this tendency toward color deterioration retarded by adding thereto a small amount of stabilizing agent such as thiourea or an alkyl tin compound. While alkyl borates may also be employed as stabilizers for the aromatic amines, they are not as efiective as the thioureas or the alkyl tin compounds.
Thus, I have found that adding from 0.01 to 1.0% by weight, and preferably, 0.05 to 0.5% by weight, of a stabilizer such as ethylene thiourea, dibutyl tin oxide, dibutyl tin dilaurate, triethyl borate, tributyl borate to the aromatic amine the tendency toward color deterioration thereof during storage is substantially retarded. While this invention is applicable to any aromatic amine having a tendency to darken during storage such as, for example, aniline, alkyl anilines, halogen substituted anilines, toluidines and naphthylamines, it is particularly applicable in connection with the color stabilizing of m-chloroaniline.
The following example, which is given by way of illns tration only, is given to demonstrate the advantage of this invention.
EXAMPLE To portions of freshly distilled m-chloroaniline is added one of the stabilizing compounds, ethylenethiourea, dibutyl tin oxide, dibutyl tin laurate, triethyl borate and tributyl borate, in an amount of 0.1% by weight on the "ice Storage tests on m-chloroaniline Optical Density after storage at186 r2 Stabilizer, 0.1% Concentration 0 hours 96 hours 288 hours ntrol 3 98 Ethylene Thlonrea. 3 19 52 Dibutyl Tin Oxide 3 21 59 Dibut-yl Tin Dilanrate 3 19 68 Triethyl Borate 3 57 82 Tributyl Borate 3 50 79 1 Optical densities were determined on a General Electric Luxirneter scale reading 0-100, with distilled water used to standardize the meter at 0 reading.
It will be seen from the above table that ethylene thiourea, dibutyl tin oxide and dibutyl tin dilaurate give excellent results as color stabilizers for the aromatic amines, whereas triethyl borate and tributyl borate retard color deterioration to a much more limited extent.
It is to be understood that the foregoing detailed description is merely given by way of illustration and that many variations may be made therein without departing from the spirit of my invention.
Having described my invention, what I desire to secure by Letters Patent is:
1. Process for retarding the color deterioration of m-chloroaniline, which comprises adding to the m-chloroaniline 0.1% by weight, on the weight of the m-chloroaniline, of dibutyl tin oxide as the sole stabilizing agent.
2. Process for retarding the color deterioration of m-chloroaniline, which comprises adding to the m-chloroaniline 0.1% by weight, on the weightof the m-chloroaniline, of dibutyl tin dilaurate as the sole stabilizing agent.
3. A color stable m-chloroaniline consisting essentially of m-chloroaniline having incorporated therein 0.1%
by weight, on the weight of the m-chloroaniline, of dibutyl tin oxide.
4. A color stable m-chloroaniline consisting essentially of m-chloroaniline having incorporated therein 0.1% by weight, on the weight of the m-chloroaniline, of dibutyl tin dilaurate.
References Cited in the file of this patent UNITED STATES PATENTS 2,047,144 Kharasch July 7, 1936 2,123,928 Bousquet July 19, 1938 2,373,049 Pedersen Apr. 3, 1945 2,422,503 Smith June 17, 1947 2,655,543 Linch Oct. 13, 1953 2,691,681 Linch Oct. 12, 1954 2,789,103 Weinberg et al. Apr. 16, 1957

Claims (2)

1. PROCESS FOR RETARDING THE COLOR DETERIORATION OF M-CHLOROANILINE, WHICH COMPRISES ADDING TO THE M-CHLOROAMILINE 0.1% BY WEIGHT, ON THE WEIGHT OF THE M-CHLOROANILINE, OF DIBUTYL TIN OXIDE AS THE SOLE STABILIZING AGENT.
2. PROCESS FOR RETARDING THE COLOR DETERIORATION OF M-CHLOROANILINE, WHICH COMPRISES ADDING TO THE M-CHLOROANILINE, 0.1% BY WEIGHT, ON THE WEIGHT OF THE M-CHLOROANILINE, OF DIBUTYL TIN DILAURATE AS THE SOLE STABILIZING AGENT.
US605944A 1956-08-24 1956-08-24 Stabilization of aromatic amines Expired - Lifetime US2927136A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0029156A1 (en) * 1979-11-14 1981-05-27 Bayer Ag Process for the production of colour-stable o-chloranilin

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2047144A (en) * 1934-03-26 1936-07-07 Lilly Co Eli Stabilized epinephrine-type compound, and process of stabilizing it
US2123928A (en) * 1936-01-06 1938-07-19 Du Pont Stabilized parasiticidal composition
US2373049A (en) * 1943-02-05 1945-04-03 Du Pont Stabilization of organic substances
US2422503A (en) * 1943-12-28 1947-06-17 Standard Oil Dev Co Stabilized alkaryl amine and process for preparing
US2655543A (en) * 1950-10-06 1953-10-13 Du Pont Stabilized aromatic amines
US2691681A (en) * 1952-05-01 1954-10-12 Du Pont Stabilized alkoxy aromatic amines
US2789103A (en) * 1954-01-29 1957-04-16 Metal & Thermit Corp Rubber stabilized with hydrocarbon tin compounds

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2047144A (en) * 1934-03-26 1936-07-07 Lilly Co Eli Stabilized epinephrine-type compound, and process of stabilizing it
US2123928A (en) * 1936-01-06 1938-07-19 Du Pont Stabilized parasiticidal composition
US2373049A (en) * 1943-02-05 1945-04-03 Du Pont Stabilization of organic substances
US2422503A (en) * 1943-12-28 1947-06-17 Standard Oil Dev Co Stabilized alkaryl amine and process for preparing
US2655543A (en) * 1950-10-06 1953-10-13 Du Pont Stabilized aromatic amines
US2691681A (en) * 1952-05-01 1954-10-12 Du Pont Stabilized alkoxy aromatic amines
US2789103A (en) * 1954-01-29 1957-04-16 Metal & Thermit Corp Rubber stabilized with hydrocarbon tin compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0029156A1 (en) * 1979-11-14 1981-05-27 Bayer Ag Process for the production of colour-stable o-chloranilin

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