申请人:The Hilton-Davis Chemical Co.
公开号:US04595768A1
公开(公告)日:1986-06-17
Process comprises the combination of the three steps of condensing 3-N(R).sub.2 -4-X-benzoic acid with an aromatic or heterocyclic aldehyde, Y-CHO, under acidic conditions to produce 3-Y-5-X-6-N(R).sub.2 phthalide (II), condensing said phthalide with a compound of the formula Z-H under alkaline or acid conditions to produce 2-(.alpha.-Y-.alpha.-Z)methyl-4-X-5-N(R).sub.2 benzoic acid (III), and oxidizing said benzoic acid to produce 3-Y-3-Z-5-X-6-N(R).sub.2 phthalide (I) where: R is hydrogen, non-tertiary alkyl of one to four carbon atoms, benzyl or substituted benzyl; X is hydrogen or halo; Y is 4-R.sup.1 -3-R.sup.2 -2-R.sup.1 -phenyl, 1-R.sup.5 -2-R.sup.6 -5/6-R.sup.4 -3-indolyl, 9-R.sup.7 -3-carbazolyl, 9-julolidinyl, 3,4-dioxymethylenephenyl, 2-thienyl, 1-R.sup.8 -2-pyrrolyl, or 4-pyridinyl; and Z is 4-R.sup.1 -3-R.sup.2 -2-R.sup.1 -phenyl, 1-R.sup.5 -2-R.sup.6 -5/6-R.sup.4 -3-indolyl or 1-R.sup.8 -2-pyrrolyl which are useful as colorless precursor color formers in carbonless duplicating and in thermal marking systems. The intermediates, 3-Y-5-X-6-N(R).sub.2 phthalides (II) and 2-(.alpha.-Y-.alpha.-Z)methyl-4-X-5-N(R).sub.2 benzoic acids (III) also have utility as colorless precursor color formers in carbonless duplicating and thermal marking systems.
该过程包括以下三个步骤的组合:在酸性条件下将3-N(R).sub.2-4-X-苯甲酸与芳香族或杂环醛Y-CHO缩合,以产生3-Y-5-X-6-N(R).sub.2邻苯二酮(II),将所述邻苯二酮与式为Z-H的化合物在碱性或酸性条件下缩合,以产生2-(.alpha.-Y-.alpha.-Z)甲基-4-X-5-N(R).sub.2苯甲酸(III),将所述苯甲酸氧化,以产生3-Y-3-Z-5-X-6-N(R).sub.2邻苯二酮(I)。其中:R是氢、一至四个碳原子的非三级烷基、苄基或取代苄基;X是氢或卤素;Y是4-R.sup.1-3-R.sup.2-2-R.sup.1-苯基、1-R.sup.5-2-R.sup.6-5/6-R.sup.4-3-吲哚基、9-R.sup.7-3-咔唑基、9-茱萸啉基、3,4-二氧甲基苯基、2-噻吩基、1-R.sup.8-2-吡咯基或4-吡啶基;Z是4-R.sup.1-3-R.sup.2-2-R.sup.1-苯基、1-R.sup.5-2-R.sup.6-5/6-R.sup.4-3-吲哚基或1-R.sup.8-2-吡咯基。它们可用作无色前体彩色形成剂,用于无碳复写和热标记系统。中间体3-Y-5-X-6-N(R).sub.2邻苯二酮(II)和2-(.alpha.-Y-.alpha.-Z)甲基-4-X-5-N(R).sub.2苯甲酸(III)也具有作为无色前体彩色形成剂的实用性,用于无碳复写和热标记系统。