366
H E N R Y I,. WHEELER A N D GEORGE S . JAMIESON.
T h e greatest variation in any of the values obtained from the butter-fat is shown by the Reichert-lleissl value. In the first series of samples, the Reichert-Neissl value of the fat is higher after blowing than before, while in the second series it is just the reverse. I am unable to account for this. The variations in the other values are slight, and no definite conclusion can be drawn from them. Apparently the differences in the composition of butter-fat brought about by renovation, if any, arc minute, and a long series of comparative analyses would be necessary to develop them. For the present, reliance must be placed upon the physical tests for melted fat, as previously detailed. I am indebted to Messrs. Simons, Adams, and Law, assistants in the laboratory, by whom the analytical work was performed.
[CONTRIBUTIONSFROM T H E SHEFFIELD LABORATORY OF YALEUNIVERSITY. ]
ON SOTIE ALDEHYDE CONDENSATION PRODUCTS OF ARYLPSEUDOTHIOHYDANTOINS. BY
HEXRYL. W H E E L E R
AHD
GEORGES.
JAMIESON.
Received January 23, ~ 9 0 2 .
I N the course of our' work on the molecular rearrangement of thiocyanacetanilides it was found that certain stable pseudothiohydantoins gave diacetyl derivatives when warmed with acetic anhydride, and it was shown that these acetyl compounds did not behave like acetoacetic acid derivatives. This would seem t o indicate that the group -CO-CH2-Sis not present in t h e stable pseudothiohydantoins. I t has been shown, however, by Xndreasch2 that the nonsubstituted pseudothiohydantoln condenses with benzaldehyde and behaves like otherS compounds which contain the above group ; and we have now found that substituted pseudothiohydantoi'ns, which are t o be represented by formulas I, I1 and 111, are also capable of condensing with aldehydes and with oxalic ester. T h e stable pseudothiohydantoi'ns ( I ) therefore behave in a Wheeler and Johnson : A m . Chem.J.. 18, 1 2 1 (1902). Monatsh. Chcm.. 8, 407. ALoven : Bey. d . chem. Ges., 18, 3242 (1885); Nencki and Sieber : /bid., 17, 2278 (1884); Ginsberg and Bondzynski: Ibid.,19,1x9 (1886); Monatsh. Chem., 8,358 (188;); Andreasch: /bid.,8, 407, io, 75 (1889). 1
2
367
ARYLPSEUDOTHIOHYDANTOINS.
tautomeric manner in regard to their reactions with acetic anhydride and aldehydes. CH,-S
I
CO
CH,-S
I
C=NR
I
CH,-S
[
1
CO
C=NR
\ /
\/
I.
11.
CO
\/
NR
NH
I
C-NRR'.
N
111.
The condensation products which we have obtained vary in color from light yellow to deep red and have the properties of weak dyes ; in this they resemble the corresponding products of rhodanic acid, a-p-diketotetrahydrothiazole, and the non-substituted pseudothiohydantoin with salicylic and cinnamic aldehydes which have been described by Andreasch and Zipser.l Benzaldehyde and Phe?zylpseudothiohydaiztoi'n, C,H,CH-C-S
I I \/
CO C=NC,H,.
" Ten grams of the stable phenylpseudothiohydantoin were dissolved in about 150cc. of alcohol containing 1.2grams of sodium. To this solution 5.3 grams of benzaldehyde were added and the mixture was heated for several hours. T h e alcohol was then evaporated, water and dilute acetic acid were added and, after thorough stirring, the yellow precipitate was filtered, washed and dried. The yield of this crude material corresponded with the theoretical. For analysis the substance was crystallized from alcohol and from amyl acetate, whereupon, minute, slender, light yellow prisms separated from both solvents. They 'melted at about 251 ' - 2 5 2 ' ) and a nitrogen determination gave : Calculated for
CISH~ZONZS.
Nitrogen..
.... . . .... ..,... . ..... . , .. .... 10.0
Found.
9.9
This compound or a-keto-p-phenylimido-P-benzaltetrahydrothiazole is insoluble in water. It is fairly soluble in hot alcohol and it dissolves in hot dilute alkali but separates out again on cooling; it can be crystallized from dilute hydrochloric acid. The sodium ethylate addition product, C,,H,,ON,S.NaOC,H,, is readily obtained by mixing the constituents in alcoholic solu1
Chem. Ztg., a6, 54, 623 (1902).
368
HENRY I,. WHEELER A N D GEORGE S. JAMIESON.
tion. I t forms a bright yellow crystalline powder which melts at about 263'. Sodium determinations gave : Sodium
Found
Calculated for C18H1-OrN3SiVa
I.
I1
6.6
6.5
6.3
..........................
T h e silver salt, prepared by dissolving the condensation product in alcoholic ammonia, forms a fine, yellow, crystalline powder. .4 silver determination gave : Calculated for
Silver.
.................................
C,,HI1O?;?SAg
27.9
Found
28
2
BenzalphenylbePizylpseiidotlziohy d a r l t o ~ ~ i , C, H E C K=C - - 4 I,
LI
I
co
i
C--N
/C6H:
\/
\CH,C,H, N was obtained by heating the above sodium ethylate addition product with benzyl chloride in an alcoholic solution. Its structure was shown by the fact that the same compound results on condensing benzaldehyde with phenylbenzylpseudothiohydantoin. I t crystallized from alcohol in bunches of very light yelloiv needles and melted at 186"-187~. X nitrogen determination gave : Calculated for
Xitrogen.
................................
C?yHlaOiVgS.
7.5
Found
7.7
This condensation product is inspluble in water and alkali ; it dissolves readily in hot alcohol. Piperoizalpli eti3.'lpseudothioltydalztoi'll, C H,O,C,H,C H =C--S I 1 co C=NC,H,.
\/
"
Three grams of phenylpseudothiohydanto'in, 0.36 gram of sodium and 2.4 grams of piperonal were dissolved in alcohol and warmed for two hours. A bright yellow powder was thus obtained which, on crystallizing from alcohol, formed minute crystals melting at about 2 jg"-261~.A nitrogen determination gave : Calculated for
Nitrogen. ...............................
Cl,H1208N~S.
8.6
Found.
8.7
369
ARYLPSEUDOTHIOHYDANTOINS.
This material is difficultly soluble in alcohol and amyl acetate. I t dissolves in glacial acetic acid and in hot alkali, but it is insoluble in water. Metanitro benzalphenylpseudothiohydalztoin, NO,C,H,CH=C--S
I
1
CO C=NC,H,.
\/
NH
This was prepared in the same manner as the above. I t was obtained as a dark brick-red crystalline powder which proved to be less soluble than the preceding compounds. For analysis it was purified by boiling with alcohol and dissolving in alkali, precipitating with acetic acid and then washing with water. Thus obtained it did not melt at 290" and a nitrogen determination gave : Calculated for
Nitrogen.
..............................
CieHiiOsNsS. I 2.9
Found. 12.6
D iortlzotolylpseudothioltydalztoin, CH,--S
I
'
Fifty grams of diorthotolylthiourea and 20 grams of chloracetic acid were mixed in alcohol and the solution warmed for several hours. Upon cooling, colorless, flat prisms separated w h k h , on crystallizing from alcohol, melted at 151°-1520, and a nitrogen determination gave : Calculated for
Nitrogen.. .............................
c17HieONzS. 9.4
Found.
9.7
This hydanto'in is readily soluble in alcohol and strong acetic acid but insoluble in alkali. Benzaldiorthotolylpseudothiohydantoin, C,H,CH=C--S I
I
I
co
~=Nc,H,.
v
NC1H7
370
H E N R Y L. WHEELER A N D GEORGE
s. JAMIESOS.
This formed slender, light yellow prisms, when crystallized from alcohol, melting at 1 7 g O - 1 8 o O . I t is readily soluble in alcohol and insoluble in alkali. ?I nitrogen determination ga\-c : Calculated for Cg,H?,,OS,S.
..............................
Nitrogen.
Found
7.65
7.29
The sodiziiti ethylate additioii product. C , , I - ~ , , , C ) S , S . ~ a O C ? H ~ , was obtained as a light yellow polvder which did not melt at 275'. It was crystallized from alcohol and aiial!-zed with the following results : Calculated for C2cHro02KlSSa,
.......
. . . . . . . . . . 6.19 Pava.diitietliylaiii iizoplzciiylfliio T I I ' C C I , Kitrogen
Found. I.
11.
6.21
6.13
H2N-CS-YHC6H4K ( C H , ) ? , was prepared from p-dimethylphenylene diamine hydrochloride and ammonium thiocyanate, in the usual matiner. Chi crystallizing from alcohol, it formed a pale yellow powder which melted with effervescence at I ~ O O - I S IO , giving a red liquid. A nitrogen determination gave : Calculated for
Nitrogen. .............................
Found
CcHii
21.3s
2i.53
Pavadiniethgla.iiii~ioplzeiiylt1iioii~dniitoi'r trritl, HOCOCH,S-C( n")--NHC,;H,N( CE-1;:) l'. \\-as obtained from the above by warming with alcoholic aiiirnonium chloracetate. It separated as a light yellow, insoluble powder. Parai(inietli~lInnziiioplzeiay1pseiidotlzioli~~tiaiitoi'ri ~
CH,-S
I
CO
I
C=NC,H,N( CH,),
\ /
" T h e above thiohydantoic acid was warmed with an excess of glacial acetic acid until solution took place. The acid was then neutralized with sodium carbonate and the precipitate was washed, dried and crystallized from alcohol. I t formed a finely divided, dull yellow powder which sintered at about 210' and melted at 222'. A nitrogen determination gave: Calculated for
Nitrogen..
.....................
CilH130N3S.
Found
18.20
37=
ARYLPSEUDOTHIOHYDANTOINS.
Paranitro benxalparadimethy laminophenylpseudo thiohydantoin, O,NC,H,CH=C-S
I
I
CO C=NC,H,N(CH,),.
\/
"
Molecular quantities of paranitrobenzaldehyde, sodium ethylate and the above hydantoin were warmed for several hours in alcoholic solution. T h e alcohol was then evaporated and the residue was treated with water and acetic acid; the product was a deep red powder, insoluble in water and only slightly soluble in alcohol. For analysis it was boiled with water and alcohol. I t then melted at about 250'-252' and a nitrogen determination gave: Calculated for
Nitrogen
...............................
CieHio03N1S.
Found.
I 5.2
14.9
Pheizylpseudothiohydantoinglyoxylic acid, HOCOCOCH-S
I
CO
I
C=NC,H,.
\/
?3H Ten grams of phenylpseudothiohydantoin, I .2 grams of sodium, and I O grams of ethyl oxalate were dissolved in alcohol and allowed t o stand for two days. The solution was then heated to boiling for a few minutes and allowed to cool. T h e yellow sodium salt which separated was filtered and decomposed by dilute acetic acid. T h e product then crystallized from alcohol or amyl acetate in minute yellow crystals which melted, with effervescence, to a dark red liquid at about 221'-222'. A nitrogen determination gave : Nitrogen.
..............................
Calculated for C I HgO
