Quinone diazides phenols

Herz s Explosives. Patented in 1923 CA 18, 1573-4 (1924) BritP 207563, several compositions, such as ortho-, and para-nitrated quinone diazides of the polymeric phenols or their metallic salts either (1) as a top charge over a main (base) charge such as Tetryl, TNT, or PETN, or (2) in admixtures with other compounds. Following are the primary and nitrating compounds proposed by von Herz ... 

Percussion caps or detonators are loaded with one or more of the ortho- or para-nitrated quinone diazides of the polymeric phenols or their metallic salts. The K salt of dinitro-m-hydroxyquinone diazide is obtained from nitraminoresorcinol by treatment of the hot... 

Photosynthesis of azo-dyestuffs has been reported to be effected by the irradiation of o-quinone diazides. The reaction proceeds via the contraction of the diazide CCXV to the cyclic ketene CCXVI which adds water to form the eyclopentadiene carboxylic acid CCXYII. The latter couples with unchanged CCXV (obtained from 2-amino-l-phenol-4-sulfonic acid) to form the azo-dyestuff CCXVTII.270 Similarly, V-heterocyclic azo-dyestuffs, e.g., CCXX is obtained by the photolysis of CCXIX.275... 

The photolytic process of p-quinone diazides are of great interest since they establish a synthetic route for the preparation of a large number of phenolic compounds. CCXXII and CCXXIV are obtained on irradiation of p-quinone diazide (CCXXI) and imino-p-quinone diazide (CCXXIII) in the presence of primary alcohols,279 respectively photolysis of CCXXI in water produces hydroquinone.137 Another well-authenticated example of this reaction, is the photodecomposition of CCXXI and CCXXIII in the presence of benzene, and 2,6-dichloro-quinoneimine diazide-4 in the presence of pyridine to CCXXV, CCXXVI, and CCXXVII, respectively. 

Quinone Diazides. E. von Herz (Ref 1) proposed the use of nitrated quinone diazides and tetra-zides of polyhydric phenols or their metallic salts in percussion caps and primers, either as a top charge over a main charge (Tetryl, PETN or TNT), or in mixts with usual primary expls such as LA, MF, etc. Typical compds were 4,6-dinitro-2-quinone diazide, the K salt of dinitro-3-hydroxy quin one diazide, metallic salts of dinitro-4-hydroxyquinone diazide, the Pb salt of dinitro-3,5-dihydroxyquinone diazide, and sym-tetra-nitrodihydroxydiphenylolquinone tetrazide J.E. Burns (Ref 2) proposed the use of nitrated quinone diazides, such as the 2,6-dinitro-2-diazide, with Pb pic rate, Na nitrate, Pb thio-... 

Positive Photoresists. Positive resists are entirely different from negative resists. For the purposes of this discussion we restrict ourselves to visible-light-sensitive materials. Typically, these materials are mixtures of low-molecular-weight phenol-formaldehyde polymers and derivatives of naphtho-1,2-quinone diazide, the photosensitive component. The former is soluble in aqueous alkali, but the presence of the latter, a hydrophobic species, inhibits attack of this developer on the film. On irradiation the "sensitizer" is converted to a ketene, which, after reaction with water, forms a base-soluble carboxylic acid. Thus the irradiated part of the film is rendered soluble in the developer and it can be removed selectively. The important feature of this system is that the unirradiated areas are not swollen by the developer and the resolution of this material is quite high. It is possible to prepare gratings having several... 

The diazotization products of 2- and 4-aminophenols, -naphthols (etc.), possess a mesomeric (zwitterionic) phenolate-diazonium and quinone-diazide structure. We discussed these structures in the context of aromatic diazotization (Zollinger, 1994 Sect. 2.4) because the synthetic methods used are closely related to those used for aromatic diazonium salts. This is also the case for the diazotization of amino-di-, tri- and tetrazoles, which, in their neutral form, contain a heterocyclic NH group in the )8-position to the amino group. After diazotization, the NH group is very acidic. Following deprotonation the product corresponds to a heterocyclic diazoalkane. Similarly, the diazotization product of 4-(dicyano)methylaniline ((4-amino-phenyl)malonitrile) may lose the CH proton. This compound is, therefore, sometimes called a vinylene homolog of diazomalonitrile (Regitz and Maas, 1986, p. 205). 

Carbamyl 5 cyano 2. di azo-4,6 d i ni traphenol or 3 Carbamyl-5-cyana-2-diazo>4,6 dinitrobenzo quinone [called 4.6-Dinitro-2-diazo-phenol-dicarbonsaure-(3.5)-amid-(3) nitril-(5) or 4.6 -Dinitro-benzochinon-(1.2) diazid-(2)-dicarbon-saure-(3.5)-amid-(3)-nitril(5) in Get], ... 

Arsinic chloride-3-diazo-4-phenol or l-Arsinic chloride-3 4-quinone-3-diazide.—This has the constitution (IV), and is obtained as follows 3-Amino-4-hydroxyphenylarsinic acid, when diazotised in 5N hydrochloric acid and subsequently treated with sulphur dioxide and hydriodic acid as described above, yields a compound CgHjONaClgAs, which on solution in methyl alcohol and precipitation by ether loses 1 molecule of hydrogen chloride, giving the diazide. In this preparation 1-arsinic acidrS-diazo-4s phenol is also obtained. 

---