394 WILSON AND PICRERING : DERIVATIVES O F

XLVII.--Derivatives of Xemioxamazide. Part I. Ketonic Semioxamaxones.

By FORSYTH JAMES WILSON and ERIC CHARLES PICKERING. SEMIOXAMAZIDE, NH,*NH*CO*CO*NH,, prepared by Kerp and Unger (Ber., 1897, 30, 585), was found to react readily with alde- hydes, giving semioxamazones of the type CHR:N*NH*CO*CO*NH, ; it reacted much less readily, however, with ketones. A further investigation was carried out by Radcliffe and Loo (Perf. and Essent. Oil Rec., 1919, 10, 39), who also found that the reaction was a general one for aldehydes, but that the application to ketones was limited ; no acetone derivative, for example, could be obtained, as had been already noted by Kerp and Unger.

We have found that the reaction between semioxamazide and ketones is far more general than the literature indicates, and have worked out what appears to be a general method for the prepar- ation of such ketonic derivatives. The semioxamazones of the lower aliphatic ketones are very easily hydrolysed by water alone, so that dry solvents should be employed; in this way, the acetone derivative can be easily prepared. The reaction between ketones and semioxamazide in absolute alcohol is accelerated to a re- markable extent by the addition of a small quantity of iodine (see experimental part).

The method we have adopted is to heat on the water-bath the calculated quantities of ketone and finely powdered semioxamazide in absolute alcohol. A small quantity of iodine is added to the boiling liquid, the semioxamazide, which is insoluble in alcohol, rapidly dissolves, and the semioxamazone separates on cooling. In the case of unsaturated ketones, we have avoided the use of iodine, and have simply heated the ketone and semioxamazide in absolute alcohol until solution is complete. The use of iodine in anil formation is referred to by Knoevenagel ( J . pr . Chem., 1914, [ii], 89, 37).

We have prepared the semioxamazones of the following ketones

Publ

ishe

d on

01

Janu

ary

1923

. Dow

nloa

ded

by T

empl

e U

nive

rsity

on

29/1

0/20

14 2

0:11

:44.

View Article Online / Journal Homepage / Table of Contents for this issue

SEMIOXAMAZIDE. PART I. KETONIC SEMIOXAMAZONES. 395

-acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, rnesityl oxide, acetophenone, benzylacetone, styryl methyl ketone, and phenyl ptolyl ketone. With the excep- tion of the semioxamazones of acetophenone and styryl methyl ketone, which have been already prepared by Kerp and Unger and by Radcliffe and Loo, respectively (Zoc. c i t . ) , these derivatives do not appear to have been previously described. Styryl methyl ketone semioxamazone is markedly phototropic, rapidly changing from white to yellow on exposure to light.

The ketonic seinioxaniazones give monosodium and mono- potassium derivatives which are very readily decomposed by moisture ; these are described in the experimental part. They are presumably derived from the semioxamazone by the replace- ment of the imino-hydrogen by metal. We have also prepared a monosodium derivative of semioxarnazide itself.

We propose to continue the investigation of these semioxamaz- ones and t,heir metallic derivatives, and allso to study the action of iodine in similar reactions.

E x Y E R I M E N T A L.

dcetonesernioxamaxone, CMe,:N*NH*CO*CO*NH,.-Five grams of dry semioxamazide were heated with 30 C.C. of dry acetone on the water-bath for one hour, when the semioxamazide had completely dissolved ; in presence of a little iodine, three minutes were sufficient. The product which separated on cooling crystallised from acetone in long, white needles melting a t 147" (Found : N = 29.5. C5H,02N, requires N = 29.4 per cent.). The same substance was obtained by heating the calculated quantities of dry semioxamazide and dry acetone in absolute alcohol for forty minutes, or for two minutes in presence of a little iodine, and separated on cooling.

i iethyl Ethyl Ketone Semioxamzone, CMeEt :N*NH*CO*CO*NH,, was prepared by the same methods as the acetone derivative, in the first method forty-five minutes being required without iodine and onc minute with iodine, and in the second method, ninety minutes without iodine and three minutes with iodine. The sub- stance was recrystallised from absolute alcohol, from which it separated in small, colourless needles melting at 127" (Pound: N = 26.8. Like acetone- semioxamazone, it is hydrolysed on warming with moist ether or dilute alcohol.

C,HI1O,N, requires N = 26.7 per cent.).

J!!ethyl isoPropyl Ketone SemioxarnaxoTze, CMePrs:N*NH*CO*CO*NH,,

was prepared as in the previous cases; heating in absolute alcohol required seventy minutes without iodine and ten minutes with iodine. Recrystallisation from absolute alcohol gave colourless

Publ

ishe

d on

01

Janu

ary

1923

. Dow

nloa

ded

by T

empl

e U

nive

rsity

on

29/1

0/20

14 2

0:11

:44.

View Article Online

396 WILSON AND PIUKERING: DERIVATIVES O F

needles melting a t 143" (Pound : N = 24.7. N = 24.5 per cent.).

C,H,,O,N, requires

Methyl isoButy1 Ketone Xemioxamaxone, C,H,*CMe:N*NH*CO*CO *NH,.

-This semioxamazone is apparently not hydrolysed by water and was obtained by heating a concentrated aqueous solution of semi- oxamazide with the calculated quantity of the ketone in alcoholic solution for about half an hour, a method which was quite in- effective in the previous cases. The substance separated from the reaction mixture, on cooling, in colourless needles which, after recrystallisation from alcohol, melted a t 133" (Found : N = 22.9. C8HI5o2N3 requires N = 22.7 per cent.).

Mesityl Oxide Semioxamaxone, CMe2:CH*CMe:N*NH*CO*CO*NH2, was prepared in the same way as methyl isobutyl ketone semi- oxamazone, one hour's heating being necessary, or by heating the ketone in absolute alcohol with semioxamazide. On cooling, the semioxamazone slowly separated as a white powder, which was obtained in colourless plates, melting a t 163-164" after recrystal- lisation from alcohol (Found : N = 23.0. C8HI3O2N3 requires N = 22.9 per cent.).

Acetophenonesemioxamaxone, CPhMe:N*NH*CO*CO*NH,, has already been described by Kerp and Unger and by Radcliffe and Loo (Zoc. cit.). We have prepared it by heating the ketone with sernioxamazide in absolute alcohol without iodine (one hour) or with iodine (five minutes). Benzyhcetonesemioxamazone, CH2PhCH,*CMe:N*NH*CO*CO*NH2,

was obtained by heating 2 grams of the ketone and 1 gram of semioxamazide in 20 C.C. of absolute alcohol without iodine (three hours) or with iodine (four minutes). The semioxamzone, which separated on cooling, was washed with ether and recrystallised from alcohol, from which it was deposited in small, colourless needles melting at 125" (Found : N = 18.3, 18.1. Cl2Hl5O2N3 requires N = 18.0 per cent.).

Styryl Methyl Ketone Xemioxamaxone, CHPh:CH*CMe:N*NH*CO*CO*NH,,

was prepared by the method described by Radcliffe and Loo, who give the melting point as 211-212"; we found that it melted at 220-221" (Found: N = 18-1. Calc., N = 18.1 per cent.). It rapidly becomes yellow on exposure to light, the melting point remaining unchanged.

Phenyl p-Tolyl Ketone Semioxamaxone, C ,H ,*CPh:N*NH*CQ*CO*NH,,

obtained by heating molecular quantities of the ketone and semi- oxamazide in absolute alcohol with it little iodine, formed colour-

Publ

ishe

d on

01

Janu

ary

1923

. Dow

nloa

ded

by T

empl

e U

nive

rsity

on

29/1

0/20

14 2

0:11

:44.

View Article Online

SEMXOSBMAZJ.DE. PART I. KETONIC SEMIOXAMAZOKES. 397

less prisms melting a t 197" after recrystallisation from alcohol (Found : N = 15-0. C16H1602N3 requires N = 14.9 per cent.).

Metallic Derivatives of the Semioxantuxones and of Semioxamaxide.

These metallic derivatives were prepared by heating on the water-bath the semioxamazone or semioxamazide, dissolved or suspended in absolute alcohol, with sodium ethoxide (1 mol.), or potassium hydroxide, dissolved in absolute alcohol. The semi- oxamazone or semioxamazide, if in suspension, soon dissolved to a yellow solution, and after boiling for a short time the metallic derivative was precipitated as a powder. Sometimes the pre- cipitation was rather slow; in such a case the alcoholic solution was cooled and then poured into a large volume of dry ether. The metallic derivative was collected, washed with absolute alcohol, in which it was sparingly soluble or insoluble, and dried in a vacuum over sulphuric acid. These metallic derivatives are colourless powders with the exception of those of styryl methyl ketone semi- oxamazone, which are pale yellow, and are all decomposed more or less readily by moisture. The compounds described below were prepared.

( a ) Sodium derivative of: Acetonesemioxamaxone. Found : Na = 13.5,14.0. C,H,02N3Na

requires Na = 13.9 per cent. Methyl ethyl ketone semioxamaxone. Found : Na = 12.1.

C6H1002N3Na requires Na = 12.8 per cent.

requires Na = 11.2 per cent.

C,,H120,N3Na requires Na = 9.1 per cent.

quires Na = 18.4 per cent.

Mesityl oxide semioxamaxone. Found : Na = 10.8. C8H1,0,N3Na

Styryl methyl ketone semioxamaxone. Found : Na = 8.8, 8.9.

Semioxamaxide. Found : Na = 18.0, 18.4. C,H,O,N,Na re-

( b ) Potassium derivative of: Acetophenonesemioxamuxone. Found : K = 15.9. CloHlo02N3K

Styryl methyl ketone semiommazone. Found : K = 14.4, 14.4.

ORGANIC CHEMISTRY DEPARTMENT,

requires K = 16.0 per cent.

Cl,Hl2O,N3K requires K = 14.5 per cent.

THE ROYAL TECHNICAL COLLEGE, GLASGOW. [Received, December 28th, 1922.1

VOL. cxxm. P

Publ

ishe

d on

01

Janu

ary

1923

. Dow

nloa

ded

by T

empl

e U

nive

rsity

on

29/1

0/20

14 2

0:11

:44.

View Article Online