Bis-diazonium Derivatives

The diazonium perchlorates are extremely explosive, shock-sensitive materials when dry, some even when damp [1,2], The salt derived from diazotised p-phenylendiamine was considered to be more explosive than any other substance known in 1910 [3], Individually indexed compounds are 4-Aminobenzenediazonium perchlorate, 2304 Benzene-l,4-bis(diazonium perchlorate), 2160 Benzenediazonium perchlorate, 2232 4,4/-Biphenylenebis(diazonium) perchlorate, 3457... 

Insertion of mono- or bis(aryldiazonium) cations into the Re—bonds of the hydride complexes [ReH(CO)5 (PR3)J (PR3 = P(OEt)3, PPh(OEt)2, PPh2(OEt) =1 ) results in the formation of cationic aryldiazene complexes of the compositions [Re(HNNAr)(CO)5 (PR3) ]" or [ Re(CO)5 (PR3) 2(/r-HNNArNNH)] +. " Bifunctional diazene/diazonium derivatives which can be prepared in this way are excellent building blocks for heterobinuclear and heterotrinuclear compounds with bis(aryldiazene) bridging ligands as has been demonstrated for Re-Ru, Re-Os,... 

Anderson el. al. [34] described rotaxanes of cyclodextrins with azo dyes that were synthesized by coupling of bis-diazonium salt 1 or 2 with water-soluble 2-naphthol derivative in the presence of a- or /J-cyclodcxtrin 3 (Figure 11). The products were isolated by paper chromatography. The yield for rotaxane 4 varied from 12 to 15 % for a- and fi-CD, respectively. 

The reaction of dimedone (39) with tetraphenylbismuthonium derivatives and BTMG gave the a,a-diphenyl derivative (40). But when dimedone (39) was treated with triphenylbismuth carbonate, an ylide (41) was obtainedP This ylide was later isolated as a stable crystalline compound. This ylide (41) can also be prepared by reaction of the sodium salt of dimedone either with triphenylbismuth dichloride or with triphenylbismuth oxide. Similarly, Meldrum s acid gave the corresponding bismuthonium ylide with triphenylbismuth carbonate and with triphenylbismuth dichloride.3 36 uch ylides can also be made by decomposition of the appropriate dicarbonyl diazonium derivative in the presence of triphenylbismuthane catalysed by bis(hexafluoroacetylacetonato)copper (II) 37 These ylides react with aldehydes to give cyclopropanes, dihydrofurans and a,p-unsaturated carbonyl... 

Sulfur transfer. The reaction with arenediazonium salts leads to diaryl disulfides. Interestingly, l,l -binaphthalene-2,2 -dithiol is the only product (61% yield) in the reaction with the bis-diazonium salt derived from l,r-binaphthyl-2,2 -diamine. 

Dilution of a solution of diazonium salts in sulfuric acid with water affords triazene derivatives (95IZV1315,95RCB1269). Treatment of a bridged bis(amino) furazans 200 with nitrous acid in acetic or hydrochloric acid gives macrocyclic triazene 201 (Scheme 132) (95MI4). 

A novel result of azo coupling was observed by Bagal et al. (1992 a) when they reacted 4-phenylazophenol and its 2-methyl derivative with an excess of 4-nitroben-zenediazonium salt. They obtained a compound whose elemental analysis and H NMR, UV, and IR spectra are consistent with 4,4-bis(4 -nitrophenylazo)-cyclohexa-2,5-dienone (12.14). The replacement of an arylazo group by a more electrophilic diazonium ion had occasionally been observed before this, but the double azo coupling in the 4-position is new. 

See also ALKANETHIOLS, ALKENEBIS(SULFONIUM PERCHLORATES) allyl trifluo-ROMETHANESULFONATES, ARENEDIAZO ARYL SULFIDES BIS(ARENEDIAZO) sulfides, BIS(SULFURDIIMIDES DIAZONIUM SULFATES, DIAZONIUM SULFIDES AND DERIVATIVES METAL AMIDOSULFATES, METAL PHOSPHORUS TRISULFIDES METAL SULFATES, METAL SULFIDES, NON-METAL SULFIDES SULFONIC ACID ESTERS, SULFUR BLACK, SULFUR ESTERS THIOPHENOXIDES, XANTHATES ... 

Dihydroxy-benzol ist ein sehr reaktives Kupplungsreagenz fur Diazonium-Salze dem-entsprechend gro 3 ist die Neigung, Bis- und Tris-azo-Derivate zu bilden. 

Diiodobenzo[6 jthiophene is prepared by treating the bis(mercuric chloride) derivative with iodine. Benzo[ > jthiophenes having an iodine atom at the 4-, 5-, 6- and 7-positions are obtained in high yield from the appropriate diazonium salt by the usual replacement reactions. 

During preparation of thiophenol by addition of a cold solution of potassium O-methyldithiocarbonate to a cold solution of benzenediazonium chloride, a violent explosion accompanied by an orange flash occurred [1], This was attributed to the formation and decomposition of bis(benzenediazo) disulfide. A preparation in which the diazonium solution was added to the xanthate solution proceeded smoothly [2], See also DIAZONIUM SULFIDES AND DERIVATIVES... 

ARENEDIAZOATES BIS(ARENEDIAZO) OXIDES ARENEDIAZONIUM OXIDES ARENEDIAZODIAZO SULFIDES DIAZONIUM SULFIDES AND DERIVATIVES THIATRIAZOLES TRIAZENES AZIDES... 

The formation of by-products appears to predominate with annelated derivatives, and the desired phenanthridone is, at best, only a minor product of the copper-catalyzed decomposition of the appropriate diazonium salt. Typically (and contrary to an earlier report123), the decomposition of iV-methyl-2-naphthanilide-l -diazonium fluoro-borate (96) gives poor yields of four products 2-naphthanilide (2%), jN7-methyl-9,10-benzophenanthridone (97) (3%), 2-methyl-6,7-benziso-indoline-l-spirocyclohexa-2, 5 -diene-3,4,-dione (98) (5%), and bi-(2 - methyl - 3 - oxo - 6,7 - benzisoindoline -1 - spirocyclohexa - 2, 5 - dien-4 -yl) (99) (15%).132 133... 

Bis[2-nitrobenzoyl] and bis[4-nitrobenzoyl] tellurium dichlorides were reduced to the corresponding amino derivatives by Raney Nickel/hydrogcn or hydrazine. The bis[ami-nobenzoyl] tellurium dichlorides were converted to the hydroxy derivatives via the diazonium salts. The same hydroxy derivatives were obtained through demethylation of the methoxy compounds with aluminum trichloride3,4. 

Other syntheses of this type are exemplified by the conversion of 126 to 127 by treatment with sodium sulfide (Scheme 79) <2004T4361, CHEC-III(11.16.6.1.2)711 >, the synthesis of the tricyclic [l,2,4]triazolo[l,5-z][l,3]benzox-azine 129 by reaction of the triazolylphenol 128 with bis-trichloromethyl carbonate (Scheme 80) <1995JME2196, CHEC-III(11.16.6.1)710>, and the preparation of indolo[2,l-z]benzo[l,2,4]triazine derivatives 131 by diazotization of 2-amino- 1-aryltetrahydroindoles 130 followed by an intramolecular coupling of the diazonium group with the aryl moiety (Scheme 81) <2003H2519, CHEC-III(11.14.8.4)638>. 

Both the Sandmeyer and Meerwein reactions have been interpreted by heterolytic and homolytic mechanisms. Both reactions resemble halide replacements by involving solutions of complexes of Cu(I) with the reacting species, a diazonium compound. Cohen and Lewin have reported that a mixture of p-tolyldiazonium tetrafluoroborate and copper benzoate in aprotic solvents rapidly evolves nitrogen and forms toluene, bi(/)-tolyl), />-tolyl benzoate, and p,p-dimethylazobenzene (54). As was earlier suggested by Kochi 177), the azobenzene derivative is believed to arise from a reaction between an arylcopper species and the diazonium compound. A similar mechanism was suggested for the analogous reac-... 

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