Identification of Amidone JACOB A. SCHULDINER Customs Laboratory, U.
S. Treasury Department, Baltimore, M d .
Amidone may be identified miemchemically by the formation of crystals with a series of reagents. Tests with zinc chloroiodide, potassium hromobromide, potassium iodoiodide, mercuric bromide, cadmium iodide, and Marme reagent have been found suitable. A moup of amidone precipitant reagents are proposed for macrotesting. the characteristic crystals shown in Figure 1,B, are formed. If the amidone is in solution aud method 2 is used, a second type of
A '
MIDONE (6-dimethylamiud, 4dipheuyI-%heptanone), vanously known as Methadone, Dolophine, Adanon, 10820, and AN-148, is a new synthetic drug introduced by the German chemical industry as a substitute for morphine.
When solution is eomprete, dilute to 125 ml. Figure 2 (left) shows the type of crystalline rosettes formed when method 1 is used. Under high magnification the crystal forms look like small wineed insects. The first urecioitate of hlsck droplets disappears & the more stable cry&lline forms
a p ~ & s ~BROMOBROMIDE u ~ REAGENT.To 10.0 ml. of a saturated bromine solution in distilled water add 2.0 mams of notassium bromide. A drop of very dilute amidone solution is used, with method 1. Concentrated solutions preoipitate out in a solid mass. This reaction is very sensitive to small amounts of amidone. When the reaeent has been added a whitish orecioitste forms. Later crvstal: and rosettes, formed hy r&s of'crystals, begin to grow. Figure 2 (right), shows the individual crystals, which are typically flat with keylike structures a t each end. MERCURIC BROMIDE REAGENT, a saturated solution of mercuric bromide in cold distilled water. Method 1 is used with this reagent. Crystallization begins ~~~~~~
Amidone (base) The hydrochloride of amidone is a white crystalline substance soluble in water to the extent of about 5.0%. Amidone is a race mate and has been resolved into its levo and dextrorotary isomers. Because this drug causes and supports addiction, i t may be classified as a narcotic ( d ) . MICROCHEMICAL METHODS
The natural alkaloids and many synthetic alkaloidlike compounds can he identified microscopically by a variety of crystalline forms which they produce with alkaloidal reagents. A number of publications descrihe specific microorystalline forms useful in the identification of very minute quantities of these substances (I,3-7). The growth of crystalline forms and their h a 1 size and shape m y he controlled in various ways. To obtain reproducible crystals i t is necessary to observe carefully exact procedures, which me often entirely empirical.
~~~
~
~~
~~
~
~
I
left). MAREAGENT.Dissolve 3.0 grams of cadmium iodide in 18.0 ml. of distilled water containing 6.0 grams of pot.assium iodide. This reagent precipitates with low concentratlons of amidone hvdrochloride. A milkv-white ureciuitate is formed, which after some time crystdliliiz& into iharaEteristic irregular flahwinged rosettes. Some of these rosettes look 1ike.tiu.y flies (Figures 3, right, and 4, left). CADMIUM IouinE REAGENT, a saturated solution of cadmium iodide in cold distilled water. Method 1 is used, and a milky-white precipitate is formed immediately. Later orystdlization begins and the crystals formed
Method 1. Place a drop of a very dilute solution of amidone hydrochloride on a microscope slide. Put B drop of the appropriate reagent next to it on the slide, and draw the drops together with a small glass rod. Place a cover glass over the precipitate;
useful for s&eral days and is importarit when photomicrographs are oontcmplated. Allow the preparations to stand until characteristic crystals me formed. Method 2. In a method which works well with zinc chloroiodide reagent dry amidone is placed on a microscope slide. If a solution is t o he tested directly, evaporate i t carefully to dryness on the glass slide and place a drop of reagent over the dried material. Crystal forms develop gradually. These are usually enhanced in sise and crystal structure over those obtained by the instantaneous precipitations caused by mixing solutions directly to each other. The crystal forms will differ with varying techniques Bud therefore comparable tests should he made with kuowu samples of amidone hydrochloride. Reagents and Micro Tests. ZINC CHLOROIODIDE REAGEUT. Dissolve 20 grams of zino chloride in 10 ml. of distilled water.
298
V O L U M E . 2 1 , NO. 2, F E B R U A R Y 1 9 4 9 .,
299
2
well-known characteristic Hat, feathery, rod-branching crystals were iormed. The remaining reagents gave no ervstalliiio forms. None of the crystals obtained with morphine in any way resemhlcd the eorreqmnding amidone cryst,als. MACROCHEMICAL TESTS
The reagents given in the previous section are used. following additional reagents can he utilized:
The
Cobalt thiocyanate a 2.0% solution in distilled water. Bromine water, a saturated solution in distilled water. Concentrated aqueous ammonium hydroxide. Mayer's reagent. Sodium hydroxide, 1.0% in distilled water. Lime water, a saturated solution in distilled water.
-
Y
Figure 2.
Amidone (135 X )
A.
PomaJwm iodoiodide reagent 11. rnrus.ium~ , ~ ~ ~
are irregylar feathery-winged branches (Figure 4, right).
~
b
~
~
~
i
d
~
rosettes, often with unequal
i o erbtal f o r m were noted even after seGersl hours. The Mkmk preparntion crystallized out around the edges of the cover glass, showing well formed dendritic Hattened crystal forms, which have no comparable resemblance to the cryst& obtained with amidone and this reagent. With morphine sulfate similar comparative teste were made. A
Figure 3. Amidone (70 X )
thin hairlike ra&ates. Potassium broiobramide reagent gave a few rosettes showing Bat lathlike radiates. Potasium iodoiodide reagent gave an immediate bulky brown precipitate. Later the
1
E^..._^*_,,
. . . * " . . 2 "
B
8.-
Table I. Precipit
Amidone
Dernerol
Morphine sulfate
Marrne Reagent
zina Chloroiodide Reagent
Fot&ssium Bromoiodide Reagent
Heal mdkywhite PPt.
Heavy Eoec. yellowlah PPt.
Heavy milkywhite PPt. Noppt.
Light Noppt. Heavy Noppt. yellowish darkEoeo. brown PPt. PPt. Light N o p ~ t . Brown No ppt. white ppt., disnom. peraep or PPt. redis-
Yellow
mt.
Potaaslum
Iodo- Cadmium Mercuri iodide Iodide Bromid. Reagent Reagent Reagent
Heavy Heavy brown white ppt.rePPt. diasolvee
2.0%
(Satu;i&d)
".OH Heaw white ppt.
White ppt.
Heavy
Very heavy light ye1101R
Noppt.
Noppt.
Deep
blveppt. redissolves in &O ,
,
Noppt.
No ppt.
IkOi" hydro-
ohloride (tablets) COW.i"S hydrochloride procaine
Heavy milkywhite PPt. No ppt.
Light flooc. PPI.
No Ppt.
Noppt.
Light
No ppt.
Heavy redbrown
yellow ROCC.
Heavy milkywhite PPt. Heavy milkywhite PPt.
Dionine No ppt. (ethyl morphine hvdrochloride) Nhreeme No Ppt. hydrochloride
PPt. Heavy brown Aocc. PPt. Light yellow Aooo. PPt. Light yellow Rooo. PPt. Slmht yellowish
PPt.
-iy
