386 CHATTAWAY: ISOMERIC CHANQE OF

XLIII.-Isomeric Change of Uiacylanilides into Acyl- aminoke t ones.

By FREDERICK DANIEL CHATTAWAY.

A LARGE number of derivatives of aromatic amines in which aminic hydrogen is replaced by various atoms or groups readily undergo an intramolecular rearrangement, the substituting atom or group chang- ing place with a hydrogen atom of the nucleus. Such exchange invariably occurs between the substituting atom or group and a

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DIACYLANLLIDES INTO ACYLAMINOKETONES. 387

hydrogen attached to the nucleus in an ortho- or a para-position with respect to the amino-group, interchange between a group attached to the nikrogen and a hydrogen atom in either meta-position never having been observed. The transformations which have been most thoroughly studied are those in which alkyl, nitroxyl, or halogen radicles are con- cerned ; the ready substitution of aromatic amines by agents such as nitric acid, chlorine, or bromine is due to changes of this type which are brought about with great ease.

Although the acyl groups very readily replace aminic hydrogen, these radicles have up to the present not been observed tomigrateinto the nucleus, although the diacylanilides are well known. Such intra- molecular changes, however, can be effected readily, and the reactions, in so far as they have been studied, follow a course exactly similar to that of other analogous transformations, thus :

These intramolecular rearrangements take place a t somewhat high temperatures and under the influence of catalytic agents, hydrogen chloride being always effective, whilst in some cases zinc chlorids gives a better yield. Transference of more than one acyl group into the nucleus has, however, not yet been effected.

Owing to the reactive character of the resulting ketones, the yields are never quantitative, and resinous or tarry by-products are always produced. When acetylation or benzoylation of an aromatic amine is effected by heating the base with the acid chloride, the product is in- variably coloured and small quantities of tarry matters may be formed. This is without doubt due to the occurrence, to a slight extent, of the isomeric change under consideration, and to the foramation of resinous products from the resulting ketone.

The transformation of dibenzanilide into benzoylaminobenzophenone is the only one in which both the ortho- and the para-isomerides have been isolated in quantity, and it is this case which brings these changes into complete accord with other analogous intramolecular rearracge- ments. This transformation is the only simple method by which o-aminobenzophenone has yet been obtained.

The change of diacetanilide into acetylaminoacetophenone and of dipropiooanilide into propionylaminopropiophenone where only the para-derivatives have been satisfactorily isolated have also been studied.

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388 CHATTAWAY : ISOMERIC CHANGE OF

T r a ns f o r m a t i o n of D iace t a n i I id e i n t o A c e t y I-p-a m i n 0- a c e t o p h e n o n e,

N( CO*CH,), /\ 1 1 \/

NH*CO*CH, /\ -+ I I \/

CO*CH,

Acetanilide, when heated with an equivalent quantity of acetic anhydride or acetyl chloride for some time, yields diacetanilide, which can be obtained pure by distillation.

If diacetanilide is mixed with about 10 per cent. of dry powdered zinc chloride and heated at 150-160° for several hours, or if at this temperature, it is treated with a slow current of dry hydrogen chloride, transformation takes place, and a considerable amount of the isomeric acetyl-paminoacetophenone is produced, There are clear indications of the simultaneous formation of the isomeric acetyl-o-aminoacetophenone, but the compound cannot be isolated with certainty, very probably because during the heating it becomes hydrolysed to some extent, and then, under the influence ol the zinc chloride, reacts with the p-amino- acet ophenone simultaneously formed to produce a-p-aminophen y 1- y-lepidine. This substance is always found as a product of the reaction and, as 0. Fischer has shown (Bsr., 1886, 19, 1038), it is formed almost quantitatively when a mixture of 0- and p-aminoacetophenones is heated together with zinc chloride. Some difficulty is experienced in isolating the different products, as much tarry or resinous matter is produced which is probably formed either by some complicated condensation of the aminoketones or from the unstable aminophenylacetylenes derived from these compounds by the action of the condensing agent (compare Baeyer, Ber., 1882, 15, 2174).

The following process is found to give the best results : diacet- anilide is heated at about 140-150° for 8-10 hours and a very slow current of hydrogen chloride is passed through the melted mass ; a viscid, brown liquid is produced which solidifies on cooling, and from which acetyl-p-aminoacetophenone can be obtained by long-continued crystallisation, but as the process is very tedious the base is best extracted in the following manner. The product is completely dis- solved in excess of alcohol containing about one-third of its bulk of concentrated hydrochloric acid and hydrolysed by boiling for 6-8 hours; the resulting liquid is made slightly alkaline with caustic soda and distilled in a current of steam, which removes the aniline obtained from the untransformed diacetanilide, about 50 per cent. of the aniline used being thus recovered. The alkaline liquid in the distilling

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DIACPLANlLIDES INTO ACYLAMINOKETONES. 389

flask is cooled and the tarry residue collected, the paminoacetophen- one being obtained from this by repeated extractions with boiling water. These solutions can be decolourired by heating with animal charcoal and concentrated, if necesrary, when the para-base, Khich separates on cooling, can be extracted with ether.

If the stearn distillation is continued for some time af te r the aniline has passed over, a pale yellow distillate is obtained having a n intensely penetrating odour and reddening a pine splinter previously moistened with hydrochloric acid. This distillate undoubtedly contains a little of the ortho-base, and a yellow oil can be extracted from it by ether, but the amount produced is so extremely small tha t it cannot be identified with certainty. The yield OF p-aminoacetophenone is not good and seIdom exceeds 5 per cent, of the weight of diacetanilide used.

Wi th zinc chIoride as catalyst, the yield is better, being generally about 25 per cent. Diacetanilide is intimately mixed with about a n eighth of i ts weight of zinc chloride and heated at 150" for 12 hours. The product is poured into boiling water, washed several times to remove the zinc chloride, and then treated in the foregoing manner.

This method is similar t o tha t employed by Klingel (Bey., 1885, 18, 2687) in preparing p-aminoacetophenone, except tha t diacetanilide is used in place of acetanilide and acetic anhydride in order to demon- s t ra te the transformation, Klingel regarded the action as consisting of a direct introduction of the acetyl group into the ring without the formation of any intermediate product, There can, however, be no doubt tha t diacetanilide is formed i n his method, the p-aminoaceto- phenone being produced by the transformation of the diacetyl compound.

A number of derivatives of p-aminoacetophenone have been pre- pared; these are formed by the ordinary processes, bu t in the preparation of the nitrogen-halogen derivatives great care must be taken t o avoid the liberation OF free halogen. The chloroamino- derivatives are prepared by suspending or dissolving the acylamino- ketone in chloroform and shaking it for some time with a well-cooled solution of potassium hypochlorite containing a n excess of potassium hydrogen carbonate. On separating the chloroform sulution, drying with calcium chloride, and evaporating off the solvent in a current of dry air, a yellow, viscid liquid is left, which, if pure, at once solidifies t o a colourless, crystalline mass, on cooling and stirring with a little light petroleum.

The brornoamino-derivatives are made and treated in a similar way, using a solution of hypobromous acid to which a little freshly pre- cipitated mercuric oxide has been added to prevent any liberation of free bromine.

VOL. LXXXV. D D

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390 CHATTAWAY : ISOMERIC CHANGE OF

The compounds, unless otherwise stated, were crystallised from a

Acetyl-p chloroaminoacetophenone, CH,* CO*C,H,*NCl*CO * CH,, crys-

0,2056 liberated I from 19.5 C.C. N/10 solution. C1 (as NC1) = 16.81. CloHl,O,NC1 requires C1 (as NCl) = 16.75 per cent.

AcetyZ-p-bromoaminoacetophenone, CH,*CYO*C,H,*NBr*CO*CH,, crys- tallises from petroleum (b. p. 60-80°) in yellow, glistening, rhombic plates which melt at 83'.

0,2298 liberated I from 17.9 C.C. #/lo solution. Br (as NBr) = 31.14. C,,H,,O,NBr requires Br (as NBr) = 31-22 per cent.

P~opionyZ-p-aminoacetophenone,CH3*CO*C6H4*NH~C0 *CH;CH,,crys- tallises from alcohol in glistening, transparent, colourless prisms and melts at 136'; its composition was established by estimating the chlorine in the corresponding chloroamino-derivative.

mixture of chloroform and petroleum (b. p. 60--80°).

tallises in clusters of glistening, pearly plates and melts a t 92O.

P!ropio~~yE- p-chloroaminoc~cetophenone, CH8*CO*C6H,*&TCi*CO-CH2*CH3,

0.3020 liberated I from 26*6 C.C. N/10 solution. Cl(.as NCl) = 15.61. C11H,202NCl requires C1 (as NC1) = 15.71 per cent.

Benxoyl-p-aminoacetophenone, CH,* CO* C,H,*NH* CO*C,H,, crystal- lises from alcohol or chloroform in colourless, pearly plates me1 ting at 205'.

forms colourless, transparent plates which melt at 42'.

Benxoyl-p-chloroccminoacetophenone, CH,*CO*C,H,*NC1*CO*C6H,. Benzoyl-p-aminoacetophenone is so sparingly soluble in cold chloro-

form tha t it is better to add its alcoholic solution to potassium hypochlorite solution containing excess of hydrogen carbonate, the mixture being then shaken with a little chloroform until all the solid has disappeared. To remove the alcohol and to ensure the conversion of all the benzoyl derivative, the chloroform solution is repeatedly shaken with fresh hypochlorous acid. Benxoyl-p-chloroaminoacetophenone crys- tallises in clusters of colourless plates which melt a t 77'.

0-2511 liberated I from 18-1 C.C. #/lo solution. C1 (as NCl)= 12.77.

Benxenesdphon-p-aminoacetophenone, CH,*CO*C,H,*NH*XO,*C,H,, crystallises from alcohol in clusters of, slender, colourless needles melting at 128'.

Cl,H1202NCl requires C1 (as NC1) = 12.96 per cent.

Benxertesulp~on- p - c h l o r o a m i n o a c e ~ p ~ n o ~ , CH,*CO* C6H,4NC1*S0, C6H5,

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DIACYLANILIDES INTO ACYLAMINOKETONES. 391

forms small, colourless, transparent plates, which are apparently flattened rhombs melting at 91'.

0.1804 liberated I from 11.6 C.C. N/lO solution. C1 (as NC1) = 11.39. C14H1203NClS requires C1 (as NCl) = 11.45 per cent.

Toluene- p-sec~hon- p-ccminoacetophenone, CH3*CO*C6H,*NH*S0,*C6H;CH3,

crystallises from alcohol in colourless, transparent, flattened prisms which melt at 203'.

Toluene- p-sulphon- p-chloroaminoacetophenone, CH,. CO~C,H,*NC1*SO2*CBH;CH3,

0.2909 liberated I from 18.1 C.C. N/10 solution. C1 (as NCl)= 11.03. C,,Hl,O,NCIS requires C1 (as NC1) = 10.95 per cent.

forms clusters of irregular, colourless plates melting at 93'.

Tyana fovrnation of Dipropionani lide into Propiony I- p-aminopro- piophenone,

N( CO*C2H,)2 NH* CO *C,H, /\ /\ I I \/

Under comparable conditions, dipropionanilide is transformed into the corresponding aminoketone exactly like diacetanilide, but only propionyl-p-aminopropiophenone could be isolated from the product in any quantity, although in this case also the ortho-compound is probably formed in small amount. When hydrogen chloride is used as a catalyst, the yield is small, but it is much increased by the employment of zinc chloride. The yield is better when the propionic acid formed is not separated from the dipropionanilide, about 50 per cent, of the theoretical amount being obtained in the following manner.

Propionanilide (1 mol.) is heated at 140-150' for some hours with the equivalent amount (1 mol.) of propionic anhydride, then about a third of its weight of dry powdered zinc chloride is added and the heating continued for about twelve hours. The pale brown liquid produced, which solidifies on cooling, is washed with warm water to remove zinc chloride and hydrolysed by boiling for 8 hours with an excess of alcohol containing about one-sixth of its bulk of concentrated hydrochloric acid. A.fter distilling off the alcohol in a current of steam, the residue is made slightly alkaline with caustic soda and again distilled in steam to remove any anilide obtained from unchanged dipropionanilide. On filtering the hot alkaline liquid from a very little tarry matter, the base separates from it on cooling in pale reddish-brown plates. A further

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392 CEATTAWAY : ISOMERIC CHANGE OF

quantity can be extracted from the mother liquor by ether together with a very small amount of a pungent, oily substance which is probably the ortho-isomeride.

1D-~~iinopropiophenone as i t first separates from the alkaline liquid has a somewhat reddish-broxn colour, which is, however, due to slight impurity and can be completely removed by recrystallisation. The substance is moderately soluble in alcohol o r chloroform, and sparingly 60 in ether; it crystallises from alcohol or a mixture of alcohol and ether in thick, colourless, transparent plates which are highly refractive, acd separates from chloroform in colourless, transparent, four-sided, flattened rhombs melting at 142'. It readily dissolves in hydrochloric acid forming a very soluble hydrochloride which crystal- lises in colourlees, flattened prisms.

On mixing alcoholic solutions of p-aminopropiophenone hydro- chloride and platinic chloride, the platinichloride,

2(C,H,CO*C,H,-NH,),H2Pt CI,, crystallises out in small, flattened, bright orange-coloured prisms with domed ends, The double salt is sparingly soluble in hot water and in alcohol and blackens just above 200°, but does not melt.

Pt = 27.19. C,sH,,02N2C16Pt requires P.4 = 27-52 per cent,

0.3813 yielded 0.1037 Pt.

p-Aminopropiophenone easily dissolves in a hot dilute solution of sulphuric acid, and, on cooling, the sulphate,

2 (C,H,* CO*C,H,*NH,),H,SO,, crystallises out in glistening, colourless, pearly plates which are trans- parent when thin. On heating rapidly, it melts with decomposition a t about 223O, turning a bright red colour ; if heated slowly, it melts a few degrees lower with similar decomposition.

SO4= 24.18. 0.4716 yielded 0.2771 BaSO,. ClsH2406N2S requires SO, = 24.24 per cent.

Ace t y 1-p-aminopr opiopb enone, C,H,* COO C,H,*N H*CO* CH,, is easily prepared by adding the calculated quantity of acetic anhydride to the base, when considerable heat is developed and a crystalline mass separates. On completing the action by warming for a short time on the water-bath, freeing from acid by a dilute solution of potassium hydrogen carbonate, and repeatedly crystallising from alcohol, the com- pound is obtained in perfectly colourless, long, glistening, six-sided prisms terminated by pyramids which melt a t 175'.

Kunckell (Ber., 1900, 33, 2641), who first prepared acetyl-p-amino- propiophenone by the action of propionyl chloride on acetanilide in tho presence of a large excess of aluminium chloride, states tha t it forms pale yellow needles rrielting a t 161°, and tha t the p-"minoin-opio-

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DTACYLANILIDES INTO XCYLAMINOKETONES. 393

phenone obtained from this formed long, yellow needles melting at 1409 The colour noted in both cases is without doubt due to a slight impurity. I n this method of preparation also, it is probable tha t the aminoketone is formed by the transformation of propionylacet- anilide under the influence of the aluminium chloride, and the very low melting point given by Kunckell for the acetyl derivative (14. below that obtained by the author) seems to support this view, as in the transformation of the mixed anilide i t is almost certain tha t the acetyl group as well as the prapionyl group would be transferred t o the ring, and tha t the product, however carefully purified, would retain a Emall quantity of admixed propionyl-p-aminoacetophenone.

From the base obtained in the above transformation, a number of derivatives have been made.

The nitrogen chloride and bromide derivatives of the acylamino- propiophenones were all prepared by adding an alcobolic solution of the acylaminoketone to a cooled solution of potassium hypochlorite containing hydrogen carbonate or to a solution of hypobromous acid containing suspended mercuric oxide. I n the case of the benzoyl derivatives, a large quantity of warm alcohol was required. Acet~Z-p-chloroaminopropiophenone,C2H5*CO* C,N,*NCl*CO-CH,, crys-

stallises in colourless plates melting a t 75".

0.2262 liberated I from 20 C.C. N/10 solution. C1 (as NCI) = 15.67.

Acetyl-p-bromoaminopropiophenone, C,H,*C0.C,H,gNBr*CO*CH3,

0.2704 liberated I from 19.9 C.C. N/10 solution. Br (as NBr) = 29-42.

CllH,,02NC1 requires C1 (as NCI) = 15.71 per cent.

forms brilliant, short, yellow prisms which melt at 115'.

Cl1H,,O2NBr requires Br (as NBr) = 29.60 per cent.

PropionyEp-aminopropiophenone, C,H,*CO*C,H,-NH*CO*C, H,, crys- tallises from alcohol in slender, colourless prisms melting at 1 5 3 O ; i t is easily soluble in alcohol and chloroform, sparingly so in ligroin.

Prop'onyl -p-chloroaminopsopioplmone, C2H,*C0 * C,H,*NCl co c,H,, forms colourless, transparent plates and melts a t 80'.

0.1450 liberated I from 12.1 C.C. #/lo solution. C1 (as NC1) = 14.79. C,,H,,O,NCI requires C1 (as NC1) = 14.79 per cent.

Pro~ionyZ-p-bi.omoaminopropio~~e~one, C2H,*CO*C,H,*NBr*CO*C2H5, separates in clusters of pale yellow, elongated plates which melt at 1 20°.

Br (as NBr) = 27-96. 0.1258 liberated I from 8.8 C.C. N/10 solution. C,,H,,O,NBr requires Br (as NBr) = 28.14 per cent.

Benxo yl-paminopropiophenmce, C2H,*CO*C,H,*NH*C0 C6H5, cry&

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394 CHATTAWAY: ISOMERIC CHANGE O F

callises from alcohol, in which i t is sparingly soluble, in thin, colourless, elongated plates melting at 190'.

Benxoyl-p-chloroaminolrropiopherro~, C,H,*CO*C,H,*NCZ*CO*C,H,, crystallises in clusters of colourless, transparent plates melting at 70".

0.1323 liberated I from 9.15 C.C. .iV/lO solution. C1 (as NC1) = 12.25. C,,H,,O,NCl requires C1 (as NC1) = 12.32 per cent.

Benxoyl-p-bromoaminopropiophenone, C,H5~CO*C,~,oNBroCO*~6~5,

0.1372 liborated I from 8.2 C.C. N/10 solution. Br (as NBr) = 23.S9.

When heated quickly, all the nitrogen halogen derivatives of the acyl p-aminopropiophenones undergo transformation a t about ZOO-230°, this change being accompanied by much decomposition.

Eenzenesdphon-p-aminopropiophenone, C,H,*CO~C,H,*NH*SO,*C,H,, separates in colourless, glistening plates melting at 165'.

B e ~ z x e n e s z c ~ ~ o ~ ~ - p - c h l o r o u ~ ~ ~ n o p r o p ~ o ~ 7 ~ e n o n ~ ,

forms bright yellow, rhombic plates and melts a t 11 19

c , ,~~ , ,o2NBr requires Br (as NBr) = 24.07 per cent.

C2H5* CO*C6H4* NC1*S0,*C6H,, crystallises in colourless, transparent plates which melt at 81O.

0.1556 liberated T from 9.2 C.C. N/10 solution. C1 (as NC1) = 10.48. C,,H,,O,NClS requires C1 (as NC1) = 10.95 per cent.

T r a n s f o r m a t i o n of DibenzccniEide i n t o Benxoyl-o- a no! -p-a m i n o b e n x o p hen o n e 8,

NH*CO-C,H, NH*CO*C,H, "C6H5 h TT

It was not thought necessary in this case to isolate the dibenzanilide, as this is known to be the first product of the action of benzoyl chloride on benzanilide (Compt rend., 1853, 37, 9 0 ; Ber., 1893, 26, 2853). The transformation and isolation of the products are best effected as follows.

The equivalent quantity of benzoyl chloride (2 mols.) is added to aniline (1 mol.) and the whole heated in an oil-bath ; the temperature is gradually raised as the interaction takes place, until it reaches 220-230°, at which point it is maintained for about 20 hours, A brown liquid is thus produced, which, on cooling, sets to a viscid, tarry mass, As it is difficult to isolate the isomeric benzoylaminoketones from this, it is best to hydrolyse the whole by dissolving it in a large excess of alcohol mixed with about one-third of its volume of con-

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DIACYLANILIDES INTO ACYLAMINOKETONES. 395

centrated hydrochloric acid. Complete hydrolysis is very difficult to effect, and 14 to 16 hours’ boiling is required. After the hydrolysis is complete, steam is blown rapidly through the liquid, when the alcohol first distils over and is followed by a considerable amount of ethyl benzoate. When this has all been removed, the acid liquid is rendered distinctly alkaline with sodiiim hydroxide, and steam is again passed in ; aniline is first expelled and then o-aminobenzophenone slowly distils over and either collects as a cryst.alline solid or separates in bright yellow needles from the cooled distillate. This product is perfectly pure after one crystallisation from alcohol. The pars-compound is not volatile in steam and remains behind in the distilling flask; a con- siderable amount crystallises out on filtering and cooling the hot liquid, and a further quantity can be obtained by repeatedly extracting the tarry residue with very dilute sulphuric acid, from which, on cooling, the base crystallises in a nearly pure state. It can be obtained pure by crystallisation from water containing a few drops of sulphuric acid, in which it dissolves only sparingly, or from a.lcoho1, in which it is readily soluble.

The yields of 0- and p-aminobenzophenones are respectively about 15 per cent. and 45 per cent. of the weight of the aniline used.

As in the analogous transformations of diacetanilide and dipropion- anilide, the presence of a little zinc chloride (compare Higgin, Trans., 1882, 41, 132) facilitates the transformation, and a slightly better yield of both isomerides is obtained. The process is carried out in the manner indicated above, about 10 per cent. G f finely powdered, dry zinc chloride being added. This process of intramole- cular rearrangement, which follows a precisely similar course t o the other well-known migrations of groups from the aminic nitrogen atom into the ortho- and para-positions of the ring, could in all probability be carried to the further stage, in which two acyl groups would be intro- duced into the nucleus in these positions.

Although the use of a larger amount of benzoyl chloride (3 or 4 mols. to 1 mol. of aniline) leads to a somewhat diminished yield of the benzoyl-o- and -p-aminobenzophenones, which may be due to the occurrence of this additional transformation, yet no disubstituted product has been isolated.

The isomeric change of dibenzanilide is of further interest since it affords the only simple method yet described of preparing o-amino- benzophenone, the process described being much less laborious than that employed by Ullmann and Bleier (Bey., 1903, 35, 4273), who converted toluene-p-sulphonanthranilic acid into its chloride, and treated benzene with this compound in the presence of aluminium chloride, finally liberating the base by hydrolysis with dilute sulphuric acid.

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396 CHATTAWAY : ISOMEfiIC CHANGE OF

The following compounds have been prepared from the 0- and p-aminobenzophenones obtained in the foregoing transformation.

The chloroamino- and bromoamino-derivatives of the acylamino- benzophenones were prepared respectively by adding an alcoholic solution of the acylaminoketone to a well-cooled solution of potassium hypochlorite containing an excess of potassium hydrogen carbonate, or t o a solution of hypobromoiis acid containing a little suspended mercuric oxide ; the products mere then extracted with chloroform and t h e solution treated as previously described.

AcetyE-o-chZos.ounz.irzo benxophenone, C6H5* CO*C,H,* NCl COO CH,, separ- ates from a mixture of chloroform and petroleum i n brilliant, colour- less, flattened prisms with domed ends ; it melts at 102'.

0,2022 liberated I from 14.7 C.C. N/10 solution. C1 (as NCI) = 12.88. C,,H,,O,NCl requires C1 (as NCl) = 12.96 per cent.

A cet yZ-0- bromouminobenxophenone, C,H5 'Coo C6H,*NBrm CO CH,, crys- tallises from a mixture of chloroform and petroleum in short, trans- parent, yellow prisms melting at 121'.

0.1660 liberated I from 10.5 C.C. X / l O solution. Br (as NBr) = 25.28. C,,H,,O,NBr requires Br (as NBr) = 25.13 per cent.

C6H,*C0 C6H,*2JC1 CO*C,H,, crystallises from light petroleum in clusters of colourless, flattened prisms which melt at 107".

0.1788 liberated I from 12.6 C.C. N/10 solution. C1 (as NC1) = 12.49. C,,H,,O,NCl requires Cl (as NC1) = 12.32 per cent.

Propionyl-o-bromoaminobensophenone, C,,H,*CO*C,H,*NBr-CO.C,H,, crystallises from light petroleum in bright yellow, transparent plates melting at 90".

0.1375 liberated I from 8-15 C.C. N/10 solution. Br (as NBr) = 23.69.

Propionyl-o-chloroaminoberzxop7enone,

C,,H,,O,NBr requires Br (as NBr) = 24-07 per cent.

BenzoyZ-o-chZoroamioi5enzophenone, C6H5* CO* C,H,*NCl*CO*C,H,, separates from light petroleum in colourless, glistening, rhombic plates which melt at 98".

0.1611 liberated I from 9.7 C.C. N/10 solution. C1 (as NC1) = 10.6'7. C,,K,,O,NC1 requires C1 (as NCl) = 10.56 per cent.

AcetyZ-p-chZoroarnino6enxophefione, C6H5*CO=C,H,*NCl*CO*CH3, crys- tallises from petroleum (b. p. 60--80°) in groups of colourless, flattened, elongated plates melting at 124'.

0,2396 liberated I from 17.3 C.C. N,lO solution. C1 (as NCl) = 12.79. C,,H1,O,NC1 requires C1 (as NCl) = 12.96 per cent.

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DTACYLANILIDES INTO ACYLAMINOKETONES. 397

AcetyZ-p-bromoaminohenzophenone, C,H,9CO*C6H4*NBr*CO*CR,, is less soluble than i t s analogues in chloroform; it crystallises from a mixture of about 1 part of chloroform and 3 parts of petroleum (b. p. 6O-SO0) in groups of pale yellow, six-sided plates melting at 15 1'.

0.1 624 liberated I from 10.2 C.C. N/10 solution. Br (as NBr) = 25-11. C15Hl,0,NBr requires Br (as NBr) 2 2 5 . 1 3 per cent.

Psopiony 2- p.nm$no benxophenone, c6w, - CO*C,H, NH co C,&, crys- tallises from alcohol in clusters of thin, colourlees, elongated plates which melt a t 139'. The composition of this and other acyl deriva- tives is found by the analysis of their chloroamino-derivatives.

PropionyEp-chEoroarninobenzophenone, C,H,*CO*C6H,*NC1*CO*C2H5, separates from light petroleum in glistening, colourless, flattened prisms melting at 129'.

0.1730 liberated I horn 12 C.C. N/lO solution. C1 (as NC1) = 12.29.

Propion yl-p-bromoaminobenzoph enone, C,H,-CO*C,H,*N Br *CO*C,H5, crystallises from light petroleum in pale yellow, transparent plates which melt at 123'.

CI6H,,O2NC1 requires Cl (as NCl) = 12.32 per cent.

0.1828 liberated I from 11 C.C. N]10 solution. Br (as NBr) =24*06. C,,H,,O,NBr requires Br (as NBr) =24*08 per cent.

Benxoyl-p-chloroaminobenxophenone, C,H,* CO*C,H,*NCl* CO-C,H,, separates from petroleum (b. p. 60--80°) in clusters of small, colour- less, rhombic plates melting at 107'.

0,2382 liberated I from 14 C.C. N/10 solution. C1 (as NCl) =10*42. C,oH,,02NCl requires C1 (as NCl) = 10.56 per cent.

Benxoyz-p-bromoarninobenxophenone, C,H,*CO*C,H,.N.Br*CO*C,H,, crystallises from a mixture of chloroform and petroleum in clusters of bright yellow, transparent, rhombic plates and melts a t 9 3 O .

0.2288 liberated I from 12 C.C. X/10 solution. Br (as NBr) =20*97. C2,Hl,0,NBr requires Br (as NBr) = 21-03 per cent.

Benxenasulphon-p.aminobenzophenone, C,H,*CO*C,H,*NH*SO,*C,H,, crystallises from alcohol in colourless, transparent plates and melts at 156'.

Benxenesulp~on- p-chloroamino Benxophenone, CGH5* CO*C,H,*NCl* SO,*C,H,,

separates from a mixture of chloroform and petroleum in coIourless, short, flattened prisms which melt a t 114'.

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398 GREEN AND PERKIN:

0.2969 liberated I from 16 C.C. N/10 solution. C1 (as NC1) =9*55. C,,H,,O,NClS requires C1 (as NC1) = 9.54 per cent.

!To Zuens- p-szclp~on- p-aminobenxop~enone, C,H,*CO* C,H,*NH *SO,* C,H,-CH,,

crystallises from alcohol in colourless, thin, flattened prisms melting at 184'.

~oluene-p-sulpl~on-p-cl~loi.oaminobenxo~T~enone, C,H,*CO*C,H,*NCt.SO,* C,H,*CH,,

crystallises from a mixture of chloroform and petroleum in clusters of somewhat irregular, colourless plates melting a t 11 6'.

0.3264 liberated I from 16.9 C.C. N/10 solution. C1 (as NCl) =8*97, C20H,g0,NC1S requires C1 (as NC1) = 9.19 per cent,

ST, BARTHOLOMEW'S HOSPITAL AND COLLEGE, E. C.

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