US 5,965,717 AGranted

Organic pigments from twisted benzidines

AssigneeNorth Carolina State University

InventorsHarold S. Freeman, David Hinks, Jolanta Sokolowska-Gajda

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Abstract

Nonmutagenic, highly twisted derivatives of benzidine of the following formula ##STR1## useful as intermediates for the preparation of various organic pigments were obtained. The benzidine derivatives are significantly rotated about the biphenyl linkage due to bulky substituents at the R.sub.2 and/or R.sub.4 positions. Bisazomethine, disaoacetoacetanilide, disazopyrazolone, disazobenzimidazolone and disazonaphthol pigments prepared from these highly twisted benzidines exhibit hypsochromic spectral shifts relative to pigments prepared from other benzidine compounds with less twist about the biphenyl linkage, for instance, other benzidine compounds in which all four R.sub.2 and R.sub.4 represent H. Greenish-yellow, yellow, orange, red and brown pigments obtained from the twisted benzidines are nonmutagenic in the standard Ames test and Prival modification.

Claims16

Dependent claims

A nonmutagenic, highly twisted benzidine compound or acid salts thereof, wherein the benzidine compound or acid salts thereof have (1) two phenyl rings with a biphenyl linkage therebetween, and (2) a first and a second amino functional moiety with the first amino moiety on one phenyl ring para to the biphenyl linkage and the second amino moiety on the other phenyl ring para to the biphenyl linkage, and (3) at least four substituents on the two phenyl rings, wherein the substituents are selected from the group consisting of alkyl, alkoxy, hydroxyalkyl, alkoxyalkyl, aryloxy, and halogeno substituents, and mixtures thereof, with

(A) one each of two of the same alkyl, alkoxy, hydroxyalkyl, alkoxyalkyl, and aryloxy substituents present ortho respectively to each of the two amino functional groups, provided that the alkyl, alkoxy, hydroxyalkyl, and alkoxyalkyl each has a minimum of three carbons, and
(B) one each of two of the same alkyl, alkoxy, hydroxyalkyl, alkoxyalkyl, aryloxy, and halogeno substituents present ortho respectively to each side of the biphenyl linkage, provided that the alkyl, alkoxy, hydroxyalkyl, and alkoxyalkyl each has a maximum of four carbons,
and wherein (A) and (B) are para to each other for each of the two pairs of (A) and (B).

A nonmutagenic pigment prepared from a nonmutagenic, highly twisted benzidine compound or acid salts thereof, wherein the benzidine compound or acid salts thereof have (1) two phenyl rings with a biphenyl linkage therebetween, (2) a first and a second amino functional moiety with the first amino moiety on one phenyl ring para to the biphenyl linkage and the second amino moiety on the other phenyl ring para to the second amino moiety on the other phenyl ring para to the biphenyl linkage, and (3) at least four substituents on the two phenyl rings, wherein the substituents are selected from the group consisting of alkyl, alkoxy, hydroxyalkyl, alkoxyalkyl, aryloxy, and halageno substituents, and mixtures thereof, with

(A) one each of two of the same alkyl, alkoxy, hydroxyalkyl, alkoxyalkyl, and aryloxy substituents present ortho respectively to each of the two amino functional groups, provided that the alkyl, alkoxy, hydroxyalkyl, and alkoxyalkyl each has a minimum of three carbons, and
(B) one each of two of the same alkyl, alkoxy, hydroxyalkyl, alkoxyalkyl, aryloxy, and halogeno substituents present ortho respectively to each side of the biphenyl linkage, provided that the alkyl, alkoxy, hydroxyalkyl, and alkoxyalkyl each has a maximum of four carbons,
and wherein (A) and (B) are para to each other for each of the two pairs of (A) and (B).

A method of making a nonmutagenic pigment wherein the pigment has a formula selected from the group consisting of ##STR32## wherein each R.sub.1 is the same and represents C.sub.3-6 -alkyl, C.sub.3-6 -alkoxy, C.sub.3-6 -hydroxyalkyl, C.sub.3-6 -alkoxyalkyl, or aryloxy, and

each R.sub.2 is the same and represents halogen, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, C.sub.1-4 -hydroxyalkyl, C.sub.1-4 -alkoxyalkyl, or aryloxy, and
each R.sub.3 is the same and represents H or CH.sub.3, and
each R.sub.4 is the same and represents H, halogen, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, C.sub.1-4 -hydroxyalkyl, C.sub.1-4 -alkoxyalkyl, or aryloxy, and
each X is the same and represents O, S, or NH, and
each X.sub.1 is the same and represents H, CH.sub.3, OCH.sub.3, or halogen, and
each X.sub.2 is the same and represents H, OCH.sub.3, or halogen, and
each X.sub.3 is the same and represents H or halogen, and
each X.sub.4 is the same and represents H or halogen, and
each X.sub.5 is the same and represents H or halogen, and
each X.sub.6 is the same and represents H or halogen,
said method comprising:
a. providing a corresponding nonmutagenic, highly twisted benzidine compound or acid salts thereof, wherein the benzidine compound has the formula ##STR33## and the benzidine compound or acid salts thereof are correspondingly substituted with the same R.sub.1, R.sub.2, R.sub.3, and R.sub.4, and
b. reacting the nonmutagenic benzidine compound or acid salts thereof with an agent, that substitutes on each N of the nonmutagenic benzidine compound or acid salts thereof, one of each of two of the same moieties, where each moiety has the same X, X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5, and X.sub.6, and therefore that converts the nonmutagenic benzidine compound or acid salts thereof to the corresponding nonmutagenic pigment that is correspondingly substituted with the same R.sub.1, R.sub.2, R.sub.3, R.sub.4, X, X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5, and X.sub.6.

10 more elements

Dependencies are inferred from the claim text.

Facts

Application: 08/963,963Filed 4 Nov 1997
Granted: 12 Oct 1999
Term ends: Not estimatedThe source records don’t support an estimate.

Classification13 codes

C07C 217/90
Of the same non-condensed six-membered aromatic ring: the oxygen atom of at least one of the etherified hydroxy groups being further bound to a…
C07C 211/50
Having at least two amino groups bound to the carbon skeleton: with at least two amino groups bound to carbon atoms of six-membered aromatic rings…
C07C 217/84
Of the same non-condensed six-membered aromatic ring: the oxygen atom of at least one of the etherified hydroxy groups being further bound to an…
C07C 251/76
Having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms: to carbon atoms of a saturated carbon…