Copper® chloride benzaldehyde

Aluminium, 0048 Ammonium phosphinate, 4554 Barium phosphinate, 0210 f Benzaldehyde, 2731 1,4-Benzenediol, 2333 Bis(hydrazine)tin(II) chloride, 4070 Calcium acetylide, 0585 Calcium phosphinate, 3931 Chromium(II) chloride, 4052 Chromium(II) oxide, 4241 Chromium(II) sulfate, 4244 Copper(I) bromide, 0265 Diacetatotetraaquocobalt, 1780 Diisobutylaluminium hydride, 3082 f 1,2-Dimethylhydrazine, 0955... 

Benzaldehyde. There are many ways to make many types of benzaldehydes. Different benzal-dehydes give different products. I am giving the formula to the basic type. It can be modified to give a specific type of benzaldehyde. 50 g of benzyl chloride and 50 g of copper nitrate in 300 cc of water are refluxed together, in a current of carbon dioxide for 8Vi hours or until a sample tested contains very little chlorine. Extract the mixture with ether, remove the ether on a water bath, and stir or shake the remaining oil for 1 hour (shaking is best) with a saturated solution of sodium bisulfite. Let stand for 2 hours, filter with vacuo and wash with a little cold alcohol, then with cold ether. The washings are warmed with an excess of 10% sulfuric acid. The aldehyde... 

Reaction LXXXV. Simultaneous Oxidation and Hydrolysis of Monohalogen Compounds. (A., 22, 1 143, 186.)—When benzyl chloride or one of its derivatives is heated with an aqueous solution of a mild oxidising agent, such as copper nitrate, lead nitrate, etc., combined hydrolysis and oxidation occurs, and benzaldehyde or one of its derivatives is obtained. 

Aluminium, 0048 Ammonium phosphinate, 4549 Barium phosphinate, 0210 f Benzaldehyde, 2727 1,4-Benzenediol, 2326 Bis(hydrazine)tin(II) chloride, 4064 Calcium acetylide, 0582 Calcium phosphinate, 3925 Chromium(II) chloride, 4046 Chromium(II) oxide, 4235 Chromium(II) sulfate, 4238 Copper(I) bromide, 0264 Diacetatotetraaquocobalt, 1774 Diisobutylaluminium hydride, 3076 f 1,2-Dimethylhydrazine, 0951 1,2-Diphenylhydrazine, 3511 Dipotassium phosphinate, 4425 f Ethanedial, 0719 f Formaldehyde, 0415 Formic acid, 0417 Gallium(I) oxide, 4405 Glucose, 2513 f Hydrazine, 4515 Hydroxylamine, 4493 Hydroxylaminium phosphinate, 4550 Hyponitrous acid, 4464 Iron(II) chloride, 4055 Iron(II) hydroxide, 4386 Iron(II) sulfate, 4393 Fead(II) phosphinate, 4526 Fead(II) phosphite, 4530 Fithium dithionite, 4682 Magnesium, 4685 Magnesium phosphinate, 4512 Manganese(II) phosphinate, 4514 f Methylhydrazine, 0500 Phenylhydrazine, 2366 Phosphinic acid, 4498 Phosphonic acid, 4499 Phosphonium iodide, 4510 Potassium, 4640 Potassium hypoborate, 0163... 

Metal-Complex (Formazan) Dyes. The hydrazone from 2-carboxyphenylhydra-zine-4-sulfonic acid and benzaldehyde is suspended in water and then dissolved by adding aqueous sodium hydroxide to obtain pH 6.5 -7.0. This solution is added to the aqueous diazonium salt solution obtained from a typical aqueous diazotiza-tion of 4-(2-sulfooxyethylsulfonyl)-2-aminophenyl-6-sulfonic acid. The mixture is then dripped into an aqueous solution of copper sulfate, while the pH is maintained with soda at 5.5 - 6.5. After complete coupling the pH is adjusted to 1 with concentrated hydrochloric acid. The strongly acidic solution is then neutralized with alkali to pH 5.5. The copper - formazan complex is salted out along with sodium chloride, filtered, washed with dilute aqueous sodium chloride solution, and dried. A dark powder results which gives a dark blue solution in water. It consists of an electrolyte-containing powdered sodium salt of the acid 25 ... 

Bis(phenylselanyl)methyllithiums 429 (R = H) are stable till 0 °C and were initially trapped with deuterium oxide, methyl iodide and benzophenone639. a-Substituted organolithium intermediate 429 (R = Me, w-CgH ), prepared with LiTMP in THF/HMPA at — 20 °C, reacted with alkyl bromides, ethylene oxide and benzaldehyde to give products 430 in good yields (Scheme 113)640. Bis(methylselanyl)methyllithiums 431 have been allowed to react with different electrophiles to afford products 432 (Scheme 113)640. Alkylated products have been deprotected with mercury(II) chloride or copper(II) chloride/copper(II) oxide, and by oxidation with hydrogen peroxide or benzeneseleninic anhydride644. Deprotection of selenoacetals to ketones can also be performed with sulfuric acid645. 

A PEG-SCCO2 system has also been used in the aerobic oxidation of styrene (Figure 8.7). In the presence of cuprous chloride co-catalyst the reaction favours acetophenone formation, whereas in the absence of copper benzaldehyde is favoured. The catalyst could be recycled five times and it was suggested that the PEG acts to prevent the palladium catalyst from decomposing and also assists in product separation. 

The complex is obtained from tri-n-butylphosphine and copper(I) hydride, prepared by reduction of copper(I) bromide with diisobutylaluminum hydride at —50°. The complex is a useful reducing agent it reduces iodobenzene to benzene (80% yield) and benzoyl chloride to benzaldehyde (50% yield). In addition the complex reduces primary, secondary, and tertiary alkyl-, vinyl-, and arylcopper(l) compounds to the corresponding hydrocarbons in high yields, under mild conditions and with no rearrangements.1... 

The Cu(II) complex with polyaniline (emeraldine base) exhibits a higher catalytic efficiency for the dehydrogenative oxidation of cinnamyl alcohol into cin-namaldehyde. Iron(III) chloride is similarly used instead of copper(II) chloride. The catalytic system is applicable to the decarboxylative dehydrogenation of man-delic acid to give benzaldehyde. The cooperative catalysis of polyaniline and cop-per(II) chloride operates to form a reversible redox cycle under oxygen atmosphere as shown in Scheme 3.4. The copper salt contributes to not only oxidation process but also metallic doping. The reduced phenylenediamine anionic species appear to be stabilized by the metallic dopants. 

Benzaldehyde diethyl mercaptal added in one portion to a suspension of bis-(acetylacetonato)copper(II) and cupric chloride in dry tetrahydrofuran, stirred 8 hrs., and allowed to stand overnight at room temp. 3-(a-ethylthiobenzyl)-pentane-2,4-dione. Y 92% from acetylacetone in the presence of 2,6-lutidine as HCl-scavenger Y 79%. F. e. s. T. Mukaiyama et al.. Bull. Chem. Soc. Japan 43, 2549 (1970) sulfur compds. in synthetic organic diemistry, review, cf. L. Field, Synthesis 1972, 101. 

The intramolecular variant of this reaction producing carbo-cyclic derivatives has been reported. Copper(II) chloride catalyzes the Knoevenagel condensation of 2,4-pentanedione with aldehydes and tosylhydrazones (eq 13). The reagent also catalyzes the reaction of various 1,3-dicarbonyls with dithianes such as benzaldehyde diethyl dithioacetal to give the corresponding condensation products (eq 14). ... 

Highly nucleophilic aromatic compounds are capable of arylating acyl-pyridinium salts. The first example of this striking reaction was described by Koenigs and Ruppelt s ho observed the formation of 4-(/>-dimethyl-aminophenyl) pyridine from pyridine, benzoyl chloride and dimethyl-aniline in the presence of copper. Benzaldehyde is also formed s, 736 and the copper is not necessaryThe dihydropyridine (105) is probably an intermediate. Other examples of the reaction are known s, 493 but attempts to isolate the intermediates have failed , though that from dimethyl-m-toluidine may have been obtained. In contrast, the dihydropyridines (106) were isolated when indole was the nucleophile. Skatole reacted similarly, at the 2-position of the indole nucleus, giving the fully aromatic 3-methyl-2-(4 -pyridyl)indole. These reactions failed with 2- and 4-picoline . Similar reactions occur between acylpyridinium salts and pyrroles (p. 71). 

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