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Publication numberUS2828341 A
Publication typeGrant
Publication dateMar 25, 1958
Filing dateNov 1, 1955
Priority dateNov 1, 1955
Publication numberUS 2828341 A, US 2828341A, US-A-2828341, US2828341 A, US2828341A
InventorsAdams Clyde S, Cormack Marjorie J, Lou Frazier Mary
Original AssigneeNcr Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
N-halophenyl derivatives of leucauramine
US 2828341 A
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Description  (OCR text may contain errors)

United States Patent 2,828,341 i OPl E i 1 .T R' YKTWE T 43F LEUCKURAMINE Clyde S. Adams, Yellow Springs, Marjorie J. Cormack,

Dayton, :an'd -Mary lieu Frazierr spriiigfield, Ohio, as-

signors to The Nation'al Cash Register Company, Dayton, Ohio, ai corp'or'ation of Maryland No Drawing. Application November 1, 1955 Serial No. 544,376

6 Claims. (Cl. 260-570) This invention relates to the N-halophenyl derivatives of "leucauramine having the general structure :"less; which may be I used as -color reacta nts because-they :turntoa dark blue 7 orggreen blue.color on con ing llltO adsorption contact with acidic svtypesvof: inorganic-42cmikaolin, beutonite, -alunrinumgsulfate;; zeolitemateri'ahsilica Cgels, magnesium trisilioate, and zinc sulphide, among others, and are useful in solution forxprintingtin eolor on paper eoated or-filled -with such adsorbents. Qtherwise, they are very' light-stable and annospherically stable both in their leucauramine forms and in their colored states.

The great utility of these compounds, as at present known, is theirnusejntransfer.cGatings-inmanifOId record systems wherein'the irear surface of an overlying sheet of record material is coated with afcomposition containing one or more of the noveltleucauramine derivatives and the underlying sheet containing particles of the acidic reactant. In such manifoldisystems the leucauramine derivative is usually dissolved in a suitable solvent and carried as droplets in a hydrophilic colloid film coating on the rear of the ovenlyingshee't."'"When the two sheets are in contact and a printed or written impression is made on the top surface of the overlying .sheet, rupturingthe film locally so it may be adsorbed by the adidicparticles in the coating of the under sheet. Such contact will make blue or blue-green marks on the top surface of the under sheet at the points-ef'pre'ssure. Such amatiifold system is disclosed in U. S. Patent 2,112,507 which issued July 5, 1955, on the application of Barrett K. Green.

The halogenated derivatives of N-phenyl leucauramine are much more suitable for the manifold systems mentioned than the known utih'alogenated N-phenyl leucauramine, because they are less volatile, they have increased solubility in oil, and theya're much more stable com 2 pounds in the leuco form when subjected to atmospheric conditions and light.

The leucauramine derivatives also are useful in solid powdered form as one of two solid powdered materials 5 dispersedain aicoating =on"'one"'s'ide bfea record'mater'ial sheetfthe second material being one of .the acidic inorganic materials-which cause a blue'or"blue .-g reen color to appear when marked with a stylus. Such a record sheet is disclosedin U. S. Patent 2,505,470 which issued, on the application oh BarrttKtfir'een-fon April 25, 1950. "a one process of nialcing the novel compounds consists of the steps of condensing molar equivalents of Michlers hydrol and a selectediehalogenated aniline in hot ethyl alcohol; concentrating :the reaction mixture as far as necessary to cause precipitation on cooling; filtering; purifying the crude material by treating a benzene solution of it with fullers earth and activated charcoal; and then precipitating out the reaction product by the addition of petroleum ether. The general equation for this reaction is as--. follows:

* 'anesnbstnfitee eneauranime where X is a halo-substituted ianyl 'niicleus.

I Leucauramine itself :has :the structure:

(CHa)2N H N( a)2 i The novel derivatives of this'sinventiontnray be con siderecl as derivatives of leucauramine-in that one of the hydrogen atomsattached to the (UN has been replaced by a halorsubstituted phenylegroup.

. As afiist'specifimexarnple bf"the"process, consider the making of N-(o-chlorophenyl)leucauramiue:

25.6 grams (0.2 rn'olefiof o-chloraniline, and 54.0 grams (0.2 mole) of Michlers hydrol are dissolved in 200.0 grams oflethyl alcohol in a round-bottomed fla'sk, 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 'sniall amonntsbf-cdld etliyl arsenal, .The filtr'ate ma be concentrated foradditional"cropsofcrystals. i The resultant crude productis dissolve'd in J /ZJitersb'f hot'benjzene, treated with activated charcoal, and ifi'illers earth,

andfiilt'ereil. I'Thejfihrate 'is eifaporatedlo 7200, 'i'fiilliliters,v cooled, and; the reaction product precipiarea but with petroleum ether. The resultingpureematerial is a white crystalline substance. Following .is a representation of the reaction:

(CHahN. .0 81001101 7 ahN mom); v i

The m-chlorophenyl and p-chlorophenyl derivatives may be made by using in place of the o-chloroaniline used in the example, m-chloroaniline or the p-chloroaniline.

The o-bromop'henyl, m-brornophenyl, and p-bromophenyl derivatives may be made by using, instead of the chlorinated anilines, the selected brominated anilines, using the same relative molecular proportions.

The dichlorophenyl, trichlorophenyl, tetrachlorophenyl, dibromophenyl, tribromophenyl, and tetrabromophenyl derivatives may be made in the same manner by using the selected halogenated aniline in the same molecular proportions.

As a second specific example, the N-(2,4-dichlorophenyl)leucauramine, is prepared by taking:

32.4 grams (0.2 mole) of 2,4-dichloroaniline, and

54.0 grams (0.2 mole) of Michlers hydrol and dissolving in 200.0 grams of ethyl alcohol.

The rest of the procedure is identical to that given in the first specific example, according to the following and results in a white crystalline compound. The other dichloro and dibromo derivatives may be prepared according to the same procedure.

In a similar manner the trichlorophenyl, tribromophenyl, tetrachlorophenyl and tetrabromophenyl derivatives may be made simply by choosing the selected ha1o-' genated aniline for the reaction using the same molecular proportions.

Mixed types of N-chloro-bromophenyl derivatives may be made in exactly the same way by using anilines in which both bromine and chlorine are substituted in the same phenyl group.

What is claimed is:

1. The N-halophenyl derivatives of leucauramine, which derivatives have:the.general structure:

where R is taken from the group consisting of o-halo; m-halo; p-halo; 2,3-dihalo; 2,4-dahal0; 2,5-dihalo; 3,4- dihalo; 3,5-dihalo; 2,3,4-trihalo; 2,3,5-trihalo; 3,4,5-trihalo; 2,4,5-trihalo; and 2,3,4,5tetrahalo, and in which the halo substituent in any position may be taken from the group consisting of chlorine and bromine.

2. The N-halophenyl derivatives of leucauramine, which derivatives have the general structure:

( ahN- N( Ha)2 where R is taken fromthe group consisting of o-chloro; o-bromo; m-chloro; m-bromo; p-chloro; p-bromo; 2,3-dichloro; 2,3-dibromo; 2,4-dichl0ro; 2,4-dibromo; 2,5-di- 'chloro; 2,5-dibromo; 3,4-dichloro; 3,4-dibromo; 3,5-dichloro; 3,5-dibromo; 2,3,4-trich1oro; 2,3,4-tribromo; 2,3,5-trichloro; 2,3,5-tribromo; 3,4,5-trich1oro; 3,4,5-tribromo; 2,4,5-trichloro; 2,4,5-tribromo; 2,3,4,5-tetrachloro; and 2,3,4,5-tetrabromo.

3. The compound N-(2,5-dichlorophenyl)leucauramine, having the structure:

(CHa):N N(C a):

4. The compound N-(m-bromophenyl)leucauramine, having the structure:

( ahN N( a)s 5 6 5. The compound N-(m-chlorophenyl)leucauramine, 6. The compound N-(2,4-dich10rophenyl)leueaurhaving the structure: amine, having the structure;

H (CHMN H N(C a)x (CHQIN I? N(C I): 5 5 C 1%I-H 1%I-H

Non-Patent Citations
1 *None
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2981733 *May 12, 1958Apr 25, 1961Allied ChemN-bis(p-dialkylaminophenyl)methyl derivatives of nitrogen-containing saturated heterocyclic compounds
US2983756 *May 13, 1958May 9, 1961Allied ChemAliphatic amino derivatives of bis (p-dialkylaminophenyl) methane
US3001887 *Sep 20, 1957Sep 26, 1961Mead CorpPaper manufacture
US3225039 *Nov 23, 1962Dec 21, 1965Shell Oil CoN-trityl-morpholines and process for their production
US3239366 *Nov 21, 1961Mar 8, 1966Ncr CoThermotransfer sheet material and copying systems utilizing same
US3239564 *Nov 20, 1961Mar 8, 1966Reeder Earl2 n-substituted amino halobenzo-phenones
US3277173 *Jun 13, 1963Oct 4, 1966Mobay Chemical CorpProcess for preparing aromatic polyamines
US3336296 *Oct 26, 1962Aug 15, 1967American Home ProdPreparation of 5-substituted-2h-1, 4-benzodiazepin-2-one-4-oxides
US4927802 *Dec 9, 1988May 22, 1990Ppg Industries, Inc.Pressure-sensitive multi-part record unit
US5194390 *Jul 5, 1988Mar 16, 1993Miles Inc.Composition for the assay of albumin
U.S. Classification564/321, 101/491
International ClassificationB41M5/132, C09B11/00, B41M5/136, C09B11/02
Cooperative ClassificationB41M5/136, C09B11/02
European ClassificationB41M5/136, C09B11/02