S@.

1937 HENESEY-"PREPARATION OF ISATIN B Y OXIDATION OF INDIGO" 817

The importance of accurate analysis, where Incidentally, sodium nitrite can be added to
necessary, cannot be overstated in this the list of common oxidising agents.
connexion, whether it be of either the re- Finally, one other point is worth consideration
acting materials or the oxidising agent. Laxity when investigating the oxidation of a leuco-
in this direction will result in incompletc compound, viz. whether better results are
or over-oxidation and off-shade batches will obtained by adding the solution of the leuco-
follow. compound to the oxidhing agent or vice versa.

Preparation of Isatin by Oxidation of Indigo

F. HENESEY
Isatin is obtained by oxidising Indigo with a phthalein as indicator. The alkali salt solution
nitric acid-bichromate mixture (F. R. Diez & of isatin was filtered from the unreacted Indigo
Co., G.P. 229,815). According to the literature, and neutralisation of the filtrate gave a pre-
t,he oxidation is effected by the nitric acid and cipitate, which, on being atered off, washed
the bichromate oxidises the resulting nitrous and dried, was a bright red product, n1.p.
acid back to nitric acid. 200"-201" C. The yield is 95% on the Indigo
The equation representing the reaction, in one reacting; unreacted Indigo should not exceed
atage, is 8% and can be used again in the next oxidation.
cn co

The following are the theoretical molecular I n a typical experiment the quantities used
quantities required and the actual proportions were 200 g. Indigo 20% paste, 54 g. sodium
used are given for comparison. bichromate crystals, and 97 g. of 69% nitric acid,
__
'
~-
and the yield of isatin was 344 g. with 3 g.
Theorcticnl 1 Actual Indigo recovered.
lridigo 100% ... ... ... ... 3 mol. I 3 mol. The following points of interest and import-
...1
Nitric acid
sodium b i e h o i i t c cGiinls
__
...
... ...,
16 mol.
2 mol. 1 "2 E!: ance in the process were investigated-Tem-
-~ perature of oxidation; dilution of oxidation
Thus, a considerable excess of both nitric acid mixture; rate of addition of oxidation mixture,
ant1 bichromate are used, but from preliminary and rate of agitation of reacting mass.
experiments it was not possible to obtain the
maximum yield with any other quantity. (1) Effect of Temperature of Oxidalion-Above
According to the conditions of precipitation the limit of temperature already stated, viz.
of the isatin from its alkali salt, two forms are 33" C., the yields began to fall. Three experi-
apparent, one dark brown and one brick red, men ts were carried out simultaneously under
but both forms give the same uniform bright identical conditions, except that of temperature,
red product when dried. the latter being 33", 40",and 50"C. respectively.
The yields obtained were 854%, 78*3%, and
EXPERIMENTAL 73.596 respectively. The quantity of Indigo
Indigo 20% paste was mixed with one-half the recovered was practically the same in each case,
requisite quantity of bichromate crystals and a so that a t the higher temperatures oxidation is
small quantity of water. The remainder of the carried beyond the isatin stage.
bichromate was added to the nitric acid, together (2) Effect of Dilution of Oxidation Mixture-
with enough water to ensure complete solution Within reasonable limits the concentration of
of t,he bichromate. This acid solution was then the reacting materials had no effect on the
added to the Indigo mixture. Good agitation yield, but the question of good agitation pre-
was essential and, as the temperature rose, water cludes a too concentrated reaction mass. Using
cooling was used to keep the reaction tempera- t,he quantities given in the typical experiment
ture from rising above 33" C. After adding the and adding 55 C.C.of water to the nitric acid-
oxidation mixture, stirring was continued for bichromate mixture in one case and 85 C.C. of
about 30 min. and then the mass was allowed water in the other, the yields were 33-15 g. and
to settle. The isatin and unreacted Indigo, as a 33.13 g. respectively, with Indigo recovered
coarse sandy mass, settled easily and washing 4.7 g. and 4.8 g. respectively.
could be carried out by decantation, the residue
being finally filtered off. The filter-cake was (3) Effect of Rate of Agitation and Rate of
taken up with caustic alkali using phenol- Addition of Oxidation Mixture-The question
 348 STC)CKEki-"DETERMINA'I'ION O F ALliALl 1N WOOL" Sepl. 1937

of speed of itgitation is bound up wit,h the tein- this recovertd Ititligo mc\ a \&ter
peratufe requirements to some ext,ent since the it wodd be to convert, it into Indigo \'tit, whirl1
tendency to become warin, even locally, niust proceeds quite readily.
be avoided. Agitation, t,herefore, must be The acid liquors may be treiitr(1 with iilkii,li
reasonably rapid. and the chromium recovered.
The rate of a.d&tion of thc oxidising agent is Following the above litboratory c!sperinrcnt~si i
governed by temperature considerations also. la,rg.er batch of isatin was prcparecl using 50 Ib.
The rate of addition, t,hercforc, must be deter- Indigo 20% paste, 13.5 lb. sodium hi~hroniiitc
mined in practice, and depends to some extent cryst#&, 18.5 lb. of 91% nitric acid, ii,ncl 20.3 Ib.
cm the rate of n>git,at.ionand the efficiency of the water.
cooling system. The Indigo paste, 6%lb. of h i h w n i i ~ t ciir~itl
Effect of Oxnlic Acid-In some cases of oxidn- about 5 lb. water were stirretl togct,litbr in :in
tion the presence of a litt,le oxalic acid is ad- enamelled pan fitt'ed with ;I. st,irrer ;i,iitL st,ririii-
v;tntitgeous, but 0.5% on the weight of Indigo water ja,cket. A thermometer wts in t,ho react,-
paste used failed t o affect the yield in any ing mass.
direction. The temperature WW.S raised by stwin to
On completion of t~heoxidation, tho liquors 30" C. The steam was then shut, otf ;ind t,hc
were titrated against ferrous amnionium sul- cooliiig water turned on. At the same time t,lie
phate and found to have little or no further oxidation mixture, consisting of 62 lb. bi-
oxidising power. chromate and the nitric arid diluted with about
Re-oxidation of the Recovered Indigo-The 15 lb. water, was run in n t surh i b rat,e that
Indigo recovered from the oxidation was used the temperature did not exceed 35" C. The
again and a further quantity of isatin was addition required 34 hr. and t'he t,cmperittrire
obtained, although not in good yield, practically was 32"-33" C. throughont,. The reaction mass
50% of the Indigo not reacting. For example, was left overnight, then washed, filtered and the
16.5 g. of dry recovered Indigo yiclded only residue extracted with ca~isticalkali. The h i e d
3.6 g. of isatin and 8.5 g. of Indigo were Indigo recovered weighed 1 lb. 7.j oz. The
rerovered again. yield of isatin was 0 lb. 2 oz., or OS.O~oon the
From the economic point of view it is ap- Indigo reacting. The isatin was bright red and
parently not worth while to attempt, t,o oxidise practically pure, having m.p. 200.5" C.

Determination of Alkali in Wool

D. E. STOCKER
The determination of alkali in wool is not soaps, being insoluble in alcohol, arc decomposed
easy, partIy because both the -COOH and the also by terephthalic acid, so must be sepnratelj.
-CONH-groups of the protein form sodium salts determined and an allowanre inade for them.
and partly because of its pouer of adsorbing As the terephthalic acid method is not easy to
acids. Hirst and King state that reasonably manipulate, n. new and more simple method has
accurate results may be obtained by first been studied in which the alkali in extracted by
extracting wool with alcohol, then warming it an aqueous solution of boric. acid, and the
with distilled water and titrating with standard resulting sodium borate titratcd with 0.1 A'
acid in the presence of phenolphthalein. hydrochloric acid in presence of Methyl Red or
They prefer, however, the terephthalic acid Methyl Orange. This method has the advant-
method (J. Textile Insf., 1926, T101). A ages that (i) boric acid has no action on the
weighed quantity of the wool is treated with indicafors used and the adsorption of the acid
water containing a known amount of tere- by the wool does not affect the result; ( i i ) sodium
phthalic acid at 60" C. for 4 hr. A measured borate is easily removed from wool by washing
volume of standard acid is then added, the with water; and (iii) if the solution of boric
liquid filtered and excess of acid determined by acid be saturstrcl with sodium chloritlc, calcium
titration in presence of Bromophenol Blue. soaps and dyes are not extracted, so the tliffi-
Caustic soda, sodium carbonate, and soap are culty of titrating a coloured liquid does not
co-estimated as is seen from the equations- arise.
Sodium soaps and caustic1 dkitli iirr cbutr;trtetl
+ +
2NaOH C,H,( CO OH),=2H,O C,H,(CO ONa), first by means of alcohol.
+ + +
Na,C 0, C,H,( C 0OH)I =H, 0 C 0, CBH,(C0 ONa) The method is carried out t i < folio\\ s-A
2C1,Hs,C0 ONa+ C,H,(COOH)2= weighed quantity of wool is tlrietl iintl cstrrtcted
+
2CI7H,,COOH C,H,(CO ONa),
with absolute alcohol in a continiio1is extractor.
Soap and caustic alkali can be removed by a Any free caustic alkali present is tletcrniinetl by
preliminary extraction with alcohol. Calcium titrating the alcoholic extract with 0.1 N hydro-