Aldehyde 2,4-dinitrophenylhydrazine

Aldehydes 2,4-Dinitrophenylhydrazine Yellow to red spots on pale orange background... 

Separation of aldehyde dinitrophenylhydrazines by TLC and column chromatography Excess dinitrophenylhydrazine reagent and the hydrazones of acetone, formaldehyde and acetaldehyde, which occur as contaminants, can be removed prior to preparative TLC by column chromatography. Silicic acid (Merck) columns (3x2.1 cm) may be used with chloroform to elute the aldehyde dinitrophenyl-hydrazones. 

Dinitrophenylhydrazine is a very important reagent for the identification of aldehydes and ketones (pp. 342, 346). It is readily prepared from chloro-2,4-dinitrobenzene (I). In the latter compound the chlorine is very reactive in... 

Reagent A is particularly useful for the treatment of the lower aliphatic aldehydes and ketones which are soluble in water cf. acetaldehyde, p. 342 acetone, p. 346). The Recent is a very dilute solution of the dinitrophenylhydrazine, and therefore is used more to detect the presence of a carbonyl group in a compound than to isolate sufficient of the hydrazone for effective recrystallisation and melting-point determination. 

K. Treat with 2,4-dinitrophenylhydrazine reagent (pp. 263, 334). Yellow or orange-yellow precipitates given by most aldehydes and ketones. 

Method 2. Dissolve 0-25 g. of 2 4-dinitrophenylhydrazine in a mixture of 42 ml. of concentrated hydrochloric acid and 50 ml. of water by warming on a water bath dilute the cold solution to 250 ml. with distilled water. This reagent is more suitable for water-soluble aldehydes and ketones since alcohol is absent. 

If an unknown compound gives a positive test with the 2 4-dinitrophenylhydrazine reagent, it then becomes necessary to decide whether it is an aldehyde or a ketone. Although the dimedone reagent (Section 111,70,2) reacts only with aldehydes, it is hardly satisfactory for routine use in class reactions. It is much simpler to make use of three other reagents given below, the preparation and properties of which have already been described (Section 111,70). 

Cyclohexanol [108-93-0] M 100.2, m 25.2", b 161.1", d 0.946, n 1.466, n s 1.437, n 1.462. Refluxed with freshly ignited CaO, or dried with Na2C03, then fractionally distd. Redistd from Na. Further purified by fractional crystn from the melt in dry air. Peroxides and aldehydes can be removed by prior washing with ferrous sulfate and water, followed by distillation under nitrogen from 2,4-dinitrophenylhydrazine, using a short fractionating column water distils as the azeotrope. Dry cyclohexanol is very hygroscopic. 

Aldehydes, ketones Apply sample solution and moisten with 2 N 2,4-dinitrophenylhydrazine in acetic acid After reacting, dry and chromatograph the 2,4-DNPH derivatives [14]... 

The aldehyde R"CHO liberated can be determined quantitatively by means of dinitrophenylhydrazine. In the case of formaldehyde (R" = H) being split in an alcoholic-acid medium, it has been found that the formation of a dinitrophenylhydrazone is a relatively slow process. This seems to suggest that formaldehyde is originally split off in the form of an acetal which gradually yields formaldehyde under action of dinitrophenylhydrazine. 

Reagents. Methanol. This must be free from aldehydes and ketones if necessary reflux 1L of the purest material available for 2 hours with 5 g of 2,4-dinitrophenylhydrazine and five drops of concentrated hydrochloric acid. Then distil the methanol through a fractionating column and collect the fraction boiling at 64.5-65.5 °C. 

The most popular reagent for the formation of aldehyde and ketone derivatives is 2,4-dinitrophenylhydrazine which forms hydrazones containing strong chromophores. 

If a group-specific reagent is now used, e.g. one that is chosen to react specifically with the reducing properties of aldehydes (ammoniacal silver nitrate solution) or to react with ketones (2,4-dinitrophenylhydrazine [9]) it is very simple to determine which form of alcohol is present in the sample. 

Aldehydes and ketones can be located as orange or yellow zones after reaction with 2,4-dinitrophenylhydrazine hydrochloride (200 mg dissolved in 2 ml of aqueous HCl). In some cases, heating to 100°C is necessary. 

Both aldehydes and ketones contain the carbonyl group, hence a general test for carbonyl compounds will Immediately characterise both classes of compoimds. The preferred reagent is 2 4-dinitrophenylhydrazine, which gives sparingly soluble phenylhydrazones with carbonyl compounds ... 

Carbonyl compounds for instance can be trapped by absorption in a reagent solution containing 2, 4-dinitrophenylhydrazine and hydrogen chloride. Details of this method are extensively described elsewhere (8). The principle of the method is that the carbonyl compounds, in case of rendering plant emission the aldehydes, react with the 2,4-dinitrophenylhydrazine and form 2,4-dinitrophenylhydrazones (2,4-DNPH s) according to the scheme. 

A mixture of 20 g (0.1 mol) of aluminum isopropoxide, 0.1 mol of an aldehyde or a ketone and 100 ml of dry isopropyl alcohol is placed in a 250 ml flask surmounted by an efficient column fitted with a column head providing for variable reflux. The mixture is heated in an oil bath or by a heating mantle until the by-product of the reaction - acetone - starts distilling. The reflux ratio is adjusted so that the temperature in the column head is kept at about 55° (b.p. of acetone) and acetone only is collected while the rest of the condensate, mainly isopropyl cohol (b.p. 82°), flows down to the reaction flask. When no more acetone is noticeable in the condensate based on the test for acetone by 2,4-dinitrophenylhydrazine the reflux regulating stopcock is opened and most of the isopropyl alcohol is distilled off through the column. The residue in the distilling flask is cooled, treated with 200 ml of 7% hydrochloric acid and extracted with benzene the benzene extract is washed with water, dried and either distilled if the product of the reduction is volatile or evaporated in vacuo in the case of non-volatile or solid products. Yields of the alcohols are 80-90%. 

Procedures. Chromatographic Purification of Ozonization Products. Ozonization products from ethyl 10-undecenoate and 1-octene were chromatographed on silica gel columns (Baker) and eluted with 15 or 25% ether in petroleum ether (b.p., 30°-60°). Fractions were examined by thin-layer chromatography (TLC) on silica gel G Chroma-gram sheet eluted with 40% ether in petroleum ether. For development of ozonide and peroxide spots, 3% KI in 1% aqueous acetic acid spray was better than iodine. The spots (of iodine) faded, but a permanent record was made by Xerox copying. Color of die spots varied from light brown (ozonide) to purple-brown (hydroperoxide), and the rate of development of this color was related to structure (diperoxide > hydroperoxide > ozonide). 2,4-Dinitrophenylhydrazine spray revealed aldehyde spots and also reacted with ozonides and hydroperoxides. Fractions were evaporated at room temperature or below in a rotary evaporator. 

In the early days, greatest interest was focused on the acid-catalyzed hydrolysis (by hydrochloric acid in the presence of 2,4-dinitrophenylhydrazine) of Reissert compounds to aldehydes and the corresponding heterocyclic carboxylic acid derivatives. This reaction is fairly general for compounds of quinoline (178) and isoquinoline (179) (Table 18), but it is not applicable to pyridines as they rarely form Reissert compounds. The 3-hydroxyquino-line Reissert compound does not yield benzaldehyde, probably because acylation of the 3-hydroxy group prevents formation of the required cyclic intermediate (180). Some nitroquinolines and isoquinolines give low yields of benzaldehyde. Rather curiously, disub-stituted quinoline Reissert compounds yield less of the aldehyde than of the corresponding... 

Lipari, F., and S. J. Swarin, Determination of Formaldehyde and Other Aldehydes in Automobile Exhaust with an Improved 2,4-Dinitrophenylhydrazine Method, J. Chromatogr., 247, 297-306 (1982). 

See M. B. Smith, J. March in March s Advanced Organic Chemistry, 5,h ed., John Wiley and Sons, Inc., New York, 2001, p. 1347. The authors note that aldehydes can be formed if 2,4-dinitrophenylhydrazine is used. 

Results from the two experiments conducted on the aldehydes and ketones are listed in Table III as separate sets of data to illustrate the care that must be exercised in conducting and evaluating these runs. Both C02 extractions were performed under similar conditions. However, in the second run, the U-tube traps were contacted with the 2,4-dinitrophenylhydrazine derivatizing solution for longer periods of time. This modification in the analytical procedure permitted higher total mass accountabilities in the second experiment, ranging from 64.9% for isophorone to 28.7% for methyl isobutyl ketone. The recoveries from the raffinate for each of these compounds remained relatively constant. This result suggested that the trap recoveries in the first case were artificially low. 

Derivatization is a procedure in which analyte is chemically modified to make it easier to detect or separate. For example, formaldehyde and other aldehydes and ketones in air, breath, or cigarette smoke25 can be trapped and derivatized by passing air through a tiny cartridge containing 0.35 g of silica coated with 0.3 wt% 2,4-dinitrophenylhydrazine. Carbonyls are converted into the 2,4-dinitrophenylhydrazone derivative, which is eluted with 5 mL of acetonitrile and analyzed by HPLC. The products are readily detected by their strong ultraviolet absorbance near 360 nm. 

The procedures used to determine ambient carbonyl concentrations involve a collection step with silica or C18 cartridges impregnated with 2,4-dinitrophenylhydrazine. Contamination is inevitable with this system, and blanks must be used to compensate for the degree of contamination. Selection of the appropriate blank values to subtract is a difficult and uncertain process. Consequently, development of a gas chromatographic system that will resolve and respond to the low-molecular-weight aldehydes and ketones is needed. The mercuric oxide and atomic emission detectors should provide adequate response for the carbonyls. 

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