920 TILDEN AND SHEPHEARD: THE ACTION OF MAGNESIUM

XCVI.-The Action of Mctgnesium Methyl Iodide 018

dextro-Limonene Nitrosochlo.rides. By WILLIAM AUGUSTUS TILDEN and FREDERICK G EORGE SHEPREARD,

B . Sc.

THE products of the action of magnesium methyl iodide on pinene nitrosochloride were an oxime and a base resulting from the exchange of the oxygen of the nitroso-group for methyl (Tilden and Stokes, Trans., 1905, 87, 836), bul; the same reagent in contact with the limonene nitrosochlorides gives rise to changes of quite a different

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METHYL IODIDE ON DEXTRO-LIMONENE NITROSOCHLORIDES. 921

character. Limonene a- and /3-nitrosochlorides were prepared, and separated by the application of Wallach's method (Annalen, 1889,252, 108) and were separately treated with the reagent.

Fifteen grams of the nitrosochloride suspended in dry ether were mixed gradually with a quantity of the reagent prepared by adding 3.5 grams of magnesium to a solution of 25 grams of methyl iodide in 75 C.C. of dehydrated ether. After twelve hours, the product mas decomposed by the cautious addition of water and sufficient hydro- chloric acid to dissolve the precipitated magnesium hydroxide. The ethereal solution was separated and the greater part of the ether distilled off. On adding an equal volume of alcohol and cooling, a colourless, crystalline substance was deposited, the weight of which amounted altogether to about 25 per cent. of the weight of nitroao- chloride taken. The aqueous solution separated from the ether, rendered alkaline by the addition of soda and extracted with ether, yielded a yellow, viscid substance which soon darkened and became tarry.

The crystalline product from the P-nitrosochloride after recrystallisa- tion from alcohol melts at 150'. It is insoluble in alkalis and mineral acids, very soluble in ether, chloroform, or benzene, b u t less readily so in alcohol and petroleum. Bromine water and potass- ium permanganate have no action on this substance in the cold. Boiling concentrated aqueous solution of caustic potash produces no change, but alcoholic potash removes hydrogen chloride, and a yellow oil is formed which rapidly becomes brown and tarry. This compound is not reduced by zinc and acetic acid, but sodium and alcohol convert it into a yellow oil which darkens on exposure to air and from which no definite product could be obtained.

Limonene a-nitrosochloride yields by the action of magnesium methyl iodide a product which is in all respects similar t o the product just described. The melting point is, however, much lower, namely, 4 2 O , and it is more soluble in petroleum. The following are the results of analysis and estimation of molecular weight by observations of the freezing point of solutions in benzene,

Compound from Compound from B-nitrosochloride. a-nitrosochloride. -

I. 11. C per cent.. ........... 61.62 61.75 - I3 , , , , ............ 8.35 8-26 - N ,, ,, ............ 7.25 - 7.43 c1 y, ,, ............ 18.66 I 18.31 M.W. mean ......... 317 - 327

.................. + 1 3 0 * 3 O - + 2 1 3 O M. p. .................. 150" I 42O

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922 DEXTRO-LIMONENE NITROSOCHLORIDES.

The formula C20H,20N,C12 requires C = 62.02 ; H = 8.27 ; N = 7-23 ; C1= 18.34 per cent., with a molecular weight 387.

These compounds are, therefore, derived from the corresponding bimolecular nitrosochloride, (Cl,,H160.NCl)2, by removal of one atom of oxygen, and they are distinguished from it by a remarkable stability. No reagent has been found to produce from them definite derivatives except pentachloride of phosphorus, which exchanges chlorine for the remaining atom of oxygen.

Five grams of the a-compound were intimately mixed with 5 grams of the pentachloride and left at the common temperature for a day. Water and ice were then added and the semi-solid mass mas crystal- lised from acetic acid and from petroleum. The crystals form small, feathery clusters and melt at 139".

Analysis gave 6.42 per cent. of nitrogen, 31.65 per cent. of chlorine, and a molecular weight 388 as the mean of three experiments. The formula C,,H',,N,Cl, requires N = 6.35, C1= 33 *08 per cent., and M. W. = 442.

The crystals are insoluble in acids and in alkalis, but are soluble in the usual organic solvents. This compound does not react as a nitrogen chloride, as it seems to possess no oxidising power towards potassium iodide or alcohol.

The corresponding compound derived from the P-nitrosochloride mas obtained in the same way, but it could not be readily purified owing to the tendency to give up the elements of hydrogen chloride when heated with any solvent. It was obtained most nearly pure when crystallised from petroleum. I t then melted at 164" and contained 30.22 per cent. of chlorine, theory requiring 32.08.

The product resulting from the loss of hydrogen chloride from this substance was prepared by heating it with alcohol for some hours, It forms needles which melt at 148", and contains 7-59 per cent. of nitrogen and 19.51 per cent. of chlorine. The molecular weight estimated from the freezing point of the benzene solution was found to be 356 as the mean of three concordant experiments. The formula C2,H3,N2C12 requires N = 7.60 ; C1= 19.21, and M.W. = 369 [

The corresponding a-compound was obtained in the same way and crystallised from alcohol in small prisms melting at 113'.

The constitution of these compounds is not easily accounted for in view of the fact that the product obtained by the action of phosphorus pentachloride is saturated and that it does not give the reactions of a nitrogen chloride, Assuming that in the parent substance the two nitrogen at oms are linked together somewhat as follows:

[ .]D = + 220' in chloroform.

= + 134.8' in chloroform.

[ aID = + 206.5".

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DINITBOANISIDlNES AND THEIR PRODUCTS OF DIAZOTISATION. 923

5 5 the loss of one atom of oxygen would leave one of these nitrogen atoms quinquevalent, while the other would be trivalent or, what is perhaps more probable, the valency of the remaining oxygen atom would be divided between them thus :

c1 c1 CloHlf3<~-~>~loHlG.

\/ 0

The action of pentachloride of phosphorus on might be expected t o give a nitrogen chloride,

such a compound but apparently the

propenyl group on the other side of the limonene molecule-is involved in the change and a closed ring probably results,

ROYAL COLLEGE OF SCIENCE, LONDON.

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