Benzenes reactions with benzaldehydes

In the first reports on the use of esters of 4-bromo-2-butenoic acid (191a and b, crotonic acid) and of 4-bromo-3-methyl-2-butenoic acid (191c, senecioic acid), the corresponding Reformatsky reactions with benzaldehyde were performed with the old-fashioned procedure, which required heating the haloester, the aldehyde and granulated zinc in benzene/ether mixtures at reflux temperature. 

Reaction of benzaldehyde with 1 2 octanediol in benzene containing a small amount of p toluenesulfonic acid yields almost equal quantities of two products in a combined yield of 94% Both products have the molecular formula C15H22O2 Suggest reasonable structures for these products... 

The work of Hyatt on cyclotriveratrylene—derived octopus molecules contrasts with this. Of course, these species have the advantage of ligand directionality absent in the benzene-derived octopus molecules. Except for the shortest-armed of the species (i.e., n = 1), all of the complexing agents (i.e., n = 2—4) were capable of complexing alkali metal cations. Synthesis of these species was accomplished as indicated below in Eq. (7.7). These variations of the original octopus molecules were also shown to catalyze the reaction between benzyl chloride and potassium acetate in acetonitrile solution and to effect the Wittig reaction between benzaldehyde and benzyltriphenylphos-phonium chloride. 

The first quantitative study of the reaction of 4-methyl-l-(methylsulfinyl)benzene with benzaldehyde or 1,2,3,4-tetrahydronaphthalen-l-one showed that these additions proceeded with very low diastereoselectivity5. 

The reaction has been applied to nonheterocyclic aromatic compounds Benzene, naphthalene, and phenanthrene have been alkylated with alkyllithium reagents, though the usual reaction with these reagents is 12-20, and Grignard reagents have been used to alkylate naphthalene. The addition-elimination mechanism apparently applies in these cases too. A protected form of benzaldehyde (protected as the benzyl imine) has been similarly alkylated at the ortho position with butyl-lithium. ... 

Reactions of 4,7-phenanthroline-5,6-dione have been the subject of considerable study. It is reduced to 5,6-dihydroxy-4,7-phenanthroline by Raney nickel hydrogenation226,249 or by aromatic thiols in benzene,262 and oxidized by permanganate to 3,3 -bipyridyl-2,2 -dicarboxylic acid.263 It forms bishemiketals with alcohols226 and diepoxides with diazomethane.226 The diepoxides by reaction with hydrochloric acid form diols of type 57, R = Cl, which on oxidation with lead tetraacetate give 3,3 -bipyridyl diketones of type 58, R = Cl. Methyl ketones of type 58, R = H, are also obtained by lead(IV) acetate oxidation of the diol 57, R = H, obtained by lithium aluminum hydride reduction of 57, R = Cl. With phenyldiazomethane and diphenyldiazomethane the dione forms 1,3-dioxole derivatives,264,265 which readily hydrolyze back to the dione with concomitant formation of benzaldehyde and benzophenone, respectively. 

Condensation of 2-hydrazinopyrimidine (384) with an aromatic aldehyde formed the Schiff bases (386), which then cyclized with bromine to 6-bromo-l,2,4-triazolo[4,3-a]pyrimidine (383) and with carbon disulfide to 387 (92PS145). A similar cyclization was effected also on 384 to give 388 (68T2839 85FRP2549834), but the cyclization of 384 or 385 with carbon disulfide afforded 3-thiolo-l,2,4-triazolo[4,3-a]pyrimidin-7-ones 389 and 390, respectively. A small amount of the isomeric 3-thiolo-l, 2,4-triazolo[4,3-a]pyrimidin-5-one was isolated in the former case (68T2839). Reaction of 385 with benzaldehyde [67JCS(C)498] or p-chlorobenzaldehyde (90MI3) followed by oxidation with LTA in benzene afforded 391 (Scheme 73). 

Bacteriochlorins, 851 Barbituric acid metal complexes, 798 Barium alkoxides synthesis, 336 Barium complexes phthalocyanines, 863 porphyrins, 820 Becium homblei copper accumulation, 964 Benzaldehyde, 2-amino-self-condensation aza macrocycles from, 900 Benzamide, o-mercapto-metal complexes, 655 Benzamide oximes metal complexes, 274 Benzamidine, /V, V -diphenyl-metal complexes. 275 Benzene, 1,2-diamino-reactions with dicarbonyl compounds aza macrocycles from, 902 Benzene, 4 methylthionitroso-metal complexes, 804 Benzenedithiolates metal complexes, 605... 

When tetrahydropyridopyrimidinecarboxylates 541 were reacted with benzaldehyde in a melt below 40°C for 30 minutes, after which the reaction mixtures were diluted with ethanol and allowed to stand in a refrigerator at 0-5°C for a month, addition products 543 were obtained in about 20% yields (89JHC1061). If the reactions were carried out in boiling benzene in the presence of a few drops of concentrated hydrochloric acid for 5... 

Table 4. Products and yields of the reactions of benzaldehyde (149) with benzene at varying acidities.

Amino-5-aryl-l,3,4-oxadiazoles form stable N-nitrosamines (71c) which are converted into hydrazines (7ld) with zinc in acetic acid. Treatment of the hydrazine (71d) with nitrous acid yields the corresponding azide and with benzaldehyde a hydrazone is formed (B-61MI42300). On heating in benzene or in nitrobenzene, the nitrosamine (71c) undergoes the Gomberg-Bachmann reaction to yield 2,5-diaryl-l,3,4-oxadiazoles (73JCS(P1)1357). 

To a solution of 100 g. (2.0 moles) of 98 per cent sodium cyanide in 400 cc. of water, contained in a 3-1. round-bottomed llask fitted with a Hershberg stirrer (Org. Syn. 17, 31), is added IIX g. (2.2 moles) of ammonium chloride. The mixture is stirred at room temperature under a properly ventilated hood. When the ammonium chloride has dissolved, a solution of 212 g. (2.0 moles) of benzaldehyde in 400 cc. methyl alcohol is added in one portion. The reaction begins rapidly, the temperature rising to about 45°. Stirring is continued for two hours. The heterogeneous mixture, after dilution with 1 1. of water, is extracted with 1 1. of benzene, and the aqueous layer is discarded. The benzene layer is washed with three 50-cc. portions of water, and I lie aminonitrile is extracted, in the form of its hydrochloride, by shaking the benzene solution with 6 N hydrochloric acid, first with one 600-ce. portion and then with two 300-cc. portions. 

The reaction of HFeNp(dmpe)2 (Np = 2-naphthyl with benzaldehyde or propionai-dehyde takes place in benzene at RT in 12 h. The resulting hydride and acyl ligands are... 

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