US2828342A - N-(alkylhalophenyl) derivatives of leucauramine - Google Patents

Description

N-(ALKYLHALOPHENXL) DERIVATIVES OF LEUCAURAMINE Clyde S. Adams, Yellow Springs, and Marjorie I. Cormack, Dayton, Ohio, assignors to The National Cash Register Company,.,-l )ayton, Ohio, a corporation of Maryland No Drawing. Application January 10, 1956 Serial-No.-558,-194

. er i g. v c1. zoo- 579 invention relates to the c=N-(alkylhaloph enyl) derivatives-of leucaurarnine, having the; general; structure (CHa)zN tr isilicate, and zinc sulphide, among others, and are useful in solution for printing in color on paper coated or filled with such adsorbents. Otherwise, they are very lightstable and atmospherically-stable bothqin their leucauramine forms and in their colored states.

The great utility of these compounds, as at present known, is their use in transfer coatings in manifold record systems wherein the rear surface of an overlying sheet of record material is coated with a composition containing one or more of the novel leucauramine derivatives and the underlying sheet containing particles of the acidic reactant. In such manifold systems the leucauramine derivatives or mixtures of them, are usually dissolved in a-suitable solvent and carried as droplets in a hydrophilic colloid film coatingon the, rear oftheoverlying sheet. When the two sheets are in contact and a printed or written impression is made on the top surface of the overlying sheet, rupturing the film at the points of pressure, the liquid solution is released locally so it may be adsorbed by the acidic particles in or on the under sheet. Such contact will make blue or blue-green marks on the top surface of the under sheet at the points of pressure. Such a manifold system is disclosed in United States Patent 2,712,507 which issued July 5, 1955, on the application of Barrett K. Green.

These alkylhalo derivatives of N-phenyl leucauramine are much more suitable for the manifold systems mentioned than the unsubstituted known N-phenyl leucauramine, because they are less volatile, they have increased solubility in oil, and they are much more stable compounds in the leuco form when subjected to the atmosphere and'light.

The leucauramine derivatives also. are useful .in, solid powdered formas one of two solid .powdered materials 5 placed by an alkylhalo substituted phenyl group.

sheet, the second material being one of the acidic inorganic materials which cause a blue orblue-green color to appearwhen'marked with a stylus. Such a record sheet is disclosed in' jUnited StatesPatent 2,505,470 which issued, on the application ofia-Barrett K. Green, on April 25, 1950.

One process of--making the novel compounds consists of the steps ofqicondensing molar equivalents of Michlers hydrolan'd aiselected alkylhalo derivative of aniline in hot ethyhalcohol; concentrating the reaction mixture 'as far as necessary to cause precipitation on cooling; filtering;.puri fying the crude materialby heating a benzene solution of'it .with fullerswearth and activated charcoal; and then precipitatingout the reaction product by'the addition of petroleum ether. jThe general equaftion'for this reactionis as' follows:

. Michlers, ydrol alkylhalo substituted aniline (one-2N The novel derivatives of this invention may be con- 50 sidered as derivativesof leucauramine in that one of the hydrogen atoms attached tothe (1) N has been replaced by an alkylhalo substituted phenyl group.

Asa first-specificexample of theprocess, consider the making of 'N-(2-methyl;5-chlorophenyl )leucauramine;

0 in a round-bottomed flask fitted with a water-cooled reflux condenser. The solution is refluxed for four hours on a steam bath after which the solution is allowed to cool to room temperature. The crystals which have separated out are filtered off by suction and washed with small amounts of cold ethyl alcohol. The filtrate may be concentrated for additional crops of crystals. The resultant crude product is dissolved in 1% liters of hot benzene, treated with activated charcoal, and fullers earth, and filtered. The filtrate is evaporated to approximately 200 milliliters, cooled, and the reaction product precipitated out with petroleum ether. The resulting pure material is 3. a white crystalline substance. Following is a representation of the reaction:

+ non The other methylchloro and methylbromo derivatives mentioned in the first paragraph of the specification may be made by using a methylchloro or methylbromo aniline with the methyl and chloro or bromo substitue'nts'in the desired positions, in the same procedure just outlined with respect to the preparation of N-(2-methyl,5-chlorophenyl) leucaurarnine, the molecular proportions being the same.

A typical N-(methylbromophenyl)leucauramine is prepared as follows:

93 grams (0.5 mole) of aniline with the bromo and methyl substituents in the desired positions as selected from those set forth in the first paragraph of the specification.

135 grams (0.5 mole) and of Michlers hydrol are dissolved in 200 grams of ethyl alcohol and the before-mentioned procedure outlined for the preparation of the methylbromo derivatives is followed. The reaction is represented as follows:

Miehlers Hydro] Methylbromo substituted aniline (CH3)2N N(CHs) HOE l IITH X N-methylbromophenyl leucauramlne It will be obvious to those skilled in the art that the ethylhalo or higher alkylhalo homologs of N-(alkylhalophenyl) derivatives of leucauramine may be made in the same manner by use of the selected substituted aniline in the same molecular amounts.

.4 What is claimed is: 1. The derivative compounds of N-(alkylhalophenyD- leucauramine, having the general structure mN N( Hs)2 where RX is taken fromthe group consisting of Z-chloro, 3-methyl; 2-bromo,3-methyl; 2-methyl,3- chlor0; Z-methyl, S-bromo; 2-chloro,4-methyl; 2-bromo,4-methyl; Z-methyl, 4-chloro; 2-methyl,4-bromo; 2-chloro,5-methyl; Z-bromo, S-methyl; 2-methyl,5-chloro; 2-methyl,5-bromo; 3-chloro, 4-methyl; 3-bromo,4-methyl; 3-methyl,4-chloro; 3-methyl, 4-bro1no; 3-rnethyl,5-chloro; and 3-chloro,5-methyl.

2. The compound N-(Z-chloro,5-methlyphenyl)1eucauramine, having the structure 3. The compound N-(Z-metyhLS-chlorophenyl)leucauramine having the structure (CHahN-e 4. The compound N (2-methyl,4-bromophenyl)leucaurarnine, having the structure a)zN 7 References Cited in the file of this patent Ben, 35, 358-375 (1902).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 2,828,342 March 25, 1958 Clyde 5. Adams et a1.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should readas corrected below.

Column 2, line 5-, strike out "placed by an allgylhalo substituted phenyl group," and insert instead dispersed in a coating on one side of a record material column 4, line 33, for "metyhl" read methyl Signed and sealed this 27th day or May 1958.

(SEAL) Attest:

KARL AXIINE ROBERT c. WATSON Attesting Officer Conmissioner of Patents

Claims (1)

1. THE DERIVATIVE COMPOUNDS OF N-(ALKYLHALOPHENYL)LEUCAURAMINE, HAVING THE GENERAL STRUCTURE