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Org . 467
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The Preparation of Secondary Aliphatic Biazo-compounds from

Hydrazones
By A. C. Day, P. Raymond, R. M.Southam, and M. C. Whiting
Several reports to the contrary notwithstanding, 2-diazopropane is neither difficult to prepare nor unduly unstabl?.
I t w a s made by oxidation of acetone hydrazone with mercuric oxide, as originally described by Staudinger and Gaule
in 191 6 except that base-catalysis w a s found to be essential The analogous preparation of 4-diazo-ochns is
also described. The requisite hydrazones could be obtained in good yield if conditions conducive to dis3rJ-
portionation were avoided

ALTHOUGH 2-diazopropane was prepared by Staudinger
and Gaule by oxidation of acetone hydrazone with
yellow mercuric oxide and their method later used by
others,2 Applequist and Babad3 could not repeat the
procedure. They therefore used silver oxide as oxidant
a t -23" and obtained highly unstable ethereal soliltions
of the compound. Alternative routes have either
failed 4 or given a very low yield.5
€I. Staudinger and A. Gaule, B e r . , 1916, 49, 1897.
I?. C. Guha and 1). K. Sankaran, Be?.., 1937, 70, 1658.
D. E. ,4pplequist and H. Babad, J . O Y ~Ckem.,. 1962, 27,
288.
Needing 2-diazopropane frequently and in quantity as
a source of gem-dimethyl g r o ~ p s ,we
~ , followed
~ Staud-
inger and Gaule's procedure, but were unable to effect
the oxidation with either commercial or freshly precipi-
tated mercuric oxide. We likewise observed no reaction
J. R. Dyer, R. B. Randall, and H. M. Deutsch, J . 01.g.
Chwz., 1964, 29, 3423; cf. D. W. Adamson and J . Kenner, J .
Chem. SOC.,1935, 286.
G. ill. Iiaufman, J. A. Smith, G. G. Vander Stouw, and H.
Shechter, .J. Airier. Chem. Soc., 1965, 87, 985.
A. C. Day and M. C. Whiting, Proc. Clzern. SOC.,1964, 365;
Chem. Comm., 1965, 292; see also preceding Paper.
A . C. Day arid P. Raymond, unpublished work.
 View Article Online
468 J. Chem. SOC.(Cj, 1966
at -20" between ethereal acetone liydrazone and previously,s~9 and is well illustrated b:y the contrast
silver oxide which liad been rigorously washed free between the two preparations of diphenyldiazo-
from base. A t room temperature, the reaction witli methane 9910 (contrast also refs. 8 and 11). Miller has
silver oxide was vigorous, but subsequent silver- suggested that base-catalysed oxidation proceeds via
catalysed decomposition was so fast that only a faint, the conjugate base of a mercuriated hydrazone.
transient pink colour was observed. Hydrazones appear from the literature to be difficult
However, in the presence o€ a basic catalyst (0.05 to prepare free from the corresponding azines, and
equiv. of ethanolic potassium hydroxide), acetone although in certain cases part of the difficulty is due to
h~7drazonewas oxidised smoothly in ether a t 0-15" the insolubility of the azine (which may be counter-
Published on 01 January 1966. Downloaded by University of Idaho Library on 07/11/2016 08:08:17.

by yellow mercui ic oxide. Oxidation was essentially acted by use of an alcoholic co-solvent 12), the main
quantitative after 10 min. ; but yields after filtration problem is that hydrazones disproportionate, especially
from the mercury residues (which strongly catalysed the in the presence of traces of water.l39I4
decomposition of the diazo-compound) and adequate Octan-4-one hydrazone was easily made by slow
drying were usually 25--350//, . The ca. 0.2~-solutionsso addition of the ketone to an excess of hydrazine hydrate,
obtained were stable for several hours a t room temper- the product isolated b y ether extraction being S u f i -
ature or below, anti in general they were used directly. ciently pure for the oxidation. i2luch disproportionation
For experiments in which the presence of soluble mer- occurred on vacuum distillation, although with a rapid
cury compounds was detrirnen tal, or even d a n ~ e r o u s , ~rate of distillation a 20-25% yield of substantially pure
the diazo-solutiai was distilled (with very little loss) at hydrazone was obtained as a lower-boiling fraction,
-2O"jlO mm. and condensed a t - 2 3 " . Distilled solu- which was rather unstable even at -20". For acetone
tions had a half-life of ca. 3 lir. a t O", and their red colour hydrazone, the reaction between equimolecular amounts
persisted €or S-10 hr. even at 15'. of acetone azine and anhydrous hydrazine at 100"
The effect of base on the silver oxide oxidation was for 12 hr.l gave a product (85-90~/0,) of acceptable
particularly striking. Addition of a trace of solid sodium purity on rapid distillation. I t disproportionated
carbonate (0.003 mol.) to a (non-reacting) mixture of rather rapidly at room temperature or below, and was
the oxide and hydrazone in ether at -24" resulted in consequently redistilled immediately before use. Old
rapid reaction to give a 1576 yield of 2-diazopropane. samples could be regenerated by reheating them to
Even at this temperature, the filtered solution was 100" for 12 hr. before distillation. Qctan-4-one azine
highly unstable (decornposition catalysed by colloidal reacted impracticably slowly with hydrazine under
silver). these conditions.
The base-cat alysed mercuric oxide method was also A procedure for the preparation of hydrazones under
applicable to the preparation of the previously unknown mild conditions, using triethylamine as catalyst, has
4-diazo-octane, which was obtained neat as an unstable recently been described.15
red oil in 20-40:/, yield. (In this preparation, calcium
oxide was usually added as desiccant .) 4-Diazo-octane EXPERIMENTAL
decomposes rapidly, even at low temperature, to give Acetone Hydrazone.-This was obtained by Staudinger
octan-4-one azine and traces of octenes (1-5--2*57& by and Gaule's method (equimolecular quantities of acetone
gas chromatography). If thermal decomposition pro- azine l6and anhydrous hydrazine l7 kept a t 100" overnight)
ceeds via a carbenoid mechanism, it is somewhat and rapidly distilled (b. p. 122-126"; 1.4607; 85-
surprising that ketazine formation is favoured over 90%). It had a broad, medium-intensity band in the
intramolecular rearrangement such as : range 1600--1660 crn.-l (acetone azine has v,,,. 1635s
cm.-l). When the forerun and material boiling above 126"
P r n CN%.CH,*Prn 4 PrU-C:CH2*Prr14 P P C H=C H Pr" - were combined and reheated as before, more hydrazone
was obtained. Old samples, which had undergone dispro-
Considerable quantities of octanone were also found after portionation, could be satisfactorily regenerated by similar
decomposition, but whether this was formed by partial trcatinent before distillation. The compound should be
hydrolysis of the hydrazone, or whether the diazo-com- stored thoroughly dry, and redistilled immediately before
pound or the derived carbene reacted with molecular use.
oxygen or mercuric oxide is not known. Applequist 2-Diazoprofiane.-(a) Freshly redistilled acetone hydr-
azone (30 g.) in dry ether (100 ml.) was cooled t o 0" and
and Babad have described the thermal decomposition added with vigorous shaking to a cold (0") slurry of yellow
(in the presence of the silver residues) of 2-diazopropane
to give mainly acetone azine. l 2 G. Lock and I<. Stach, B E Y .1913,
, 76, B , 1251, and references
therein cited.
The desirability of a basic catalyst has been noted l3 T. Curtius and I,. Pflug, J . prakt. Chem., 1891, [2], 44, 536,
and earlier Papers; K. Heyns and A. Heins. ,4wzaZeut, 1957, 604,
C. D. Ncnitzescu and E. Solomonica, Org. Syrzfh., 1943, Coll. 133.
Yol. 11, p. 496; cf. P. D. Bartlett and I,. B. Gortler, J . Amel.. l4 L. I. Rraddock and M. L. Willard, J . O q . Cizevti., 1933, 18,
C h e m . SUC.,1963, 85, 1864. 313.
J. €3. Miller, J . Org. Chewz., 1959, 24, 560. l5 D. 13. R. Barton, R. E. O'Brien, and S. Sternhell, J . Chem.
10 L. I. Smith and K. I,. Howard, Org. Synth., Coll. Val. 111, SOC., 1962, 470.
1955, p. 351. IG T. Curtius and K. Thun, J . p r a k t . C'he~ri, 1891, [ 2 ] 44,
l1 I,. I. Smith and I I . 13. Hoehn. Org. Syuth., Coll. Vol. IIT, 161.
1955. p. 3 5 6 . l7 F. Raschig, E m . , 1910, 43, 1937.

Org.
mercuric oxide (120 g., 1-33 equiv.) in ether (350 nil.)
containing 3~-ethanolic potassium hydroxide (9 nil.).
The addition was made as rapidly as the vigour of the
reaction allowed (ca. 5 min.). Ice-cooling was maintained
throughout this and subsequent stages. After a further
5 min., with occasional swirling, the concentration of the
diazo-compound had reached its maximum, as shown
by the optical density at 500 mp (max. 0.D. 1-5-1.6/1 cm.
cell). The solution was filtered through cotton wool on to
potassium hydroxide pellets (200 g.). The sludge was
Published on 01 January 1966. Downloaded by University of Idaho Library on 07/11/2016 08:08:17.
washed with ether (2 x 75 ml.), and the washings
were combined with the original solution. After 5-10
min., the solution was refiltered (paper)on t o fresh potassium
hydroxide pellets (100 g.). A final filtration gave the solu-
tion of 2-diazopropane, which was either used directly
or, preferably, distilled. Flash distillation at - 20"/10 nim.
(bath at 1-2") and condensation a t -78" caused little or
no loss of either solvent or diazo-compound: the dark
distillation residues were largely acetone azine, but con-
tained much combined mercury which rapidly formed a
grey precipitate. Undistilled solutions remained visibly
coloured for 4 - 6 hr. a t 0" (2-3 hr. a t 15") and slowly
deposited a grey precipitate. Distilled solutions retained
thcir red colour for 8-10 hr. a t room temperature. The
decrease in intensity of the diazo-alkane band a t 500 nip
gave, for the distilled solutions, a good first-order plot
(half-life 3 hr. a t 0"). Undistilled solutions gave a log
(optical density) 7's. time plot which curved towards the
time axis. Yields, as measured by nitrogen evolution on
adding acetic acid, were 25-35;/, (-O.Ziu-solutjon), .,A
500 mp (E - 2 ) . Yields estimated by addition of an excess
of standard benzoic acid and titration with alkali were
consistently much lower (cf. ref. 3). There was very little
difierence between oxidations of acetone hydrazone with
commercial and freshly precipitated mercuric oxide.
X o attempt w a s made t o investigate fully the decom-
position products, although acetone azine and small
quantities of tetramethylethylene were always encountered
(cf. ref. 3).
( b ) FreshlJ- precipitated silver oxide was rigorously
washed free froni base with distilled water and dried.
No oxidation of ethereal acetone hydrazone at - 20" was
observed. -4t0" or higher, there was vigorous effervescence
accompanied by a transient pink coloration. Addition
of solid, anhydrous sodium carbonate ( 5 mg.) to a (non-
reacting) mixture of acetone hydrazone (1 g.) and silver
oxide (3.9 g.) in ether (12-5 ml.) a t -24" resulted i n the
immediate formation of a red solution, which dcxompostd
very rapidly. By nitrogcn evolution, on adding acid,
the yield was 15yo.
0 c t a n - 4 - m ~ Ifydvazow.-Octan-4-one (50 g., 1 inol.)
was added over 35 inin. to a stirred solution of hydrazine
hydrate (98 g., 5 mol.) in ethanol a t room temperature.
After 17 hr., the solution was diluted with water, and e s -
tracted with ether t o give octan-4-one hydraTom (44.3g.),
vmaX. (CCI,) 1 6 4 0 1 ~ and 1615m cm.-l (broad absorptions).
This was pure enough for the next reaction. Even on rapid
distillation a t 0.01 111111. with a bath temperature nut
View Article Online
469
exceeding 120", disproportionation t o octan-4-one mine
and hydrazine (the latter collected in a cold-trap) was
considerable and resulted in a continuously rising b. p.
and a contaminated product. An early fraction (20-
25%) was essentially the hydrazone, b. p. 52.6"/0.01 niin.,
3zDZ5 1.4590 (Found: C, 68.2; I-I, 12.95; N, 19.1. C,H,,N,
requires C, 67.55; €I, 12.76; S , 19-70,;); vma\-. (CCI,)
1640m and 1615m cni.-l. The later fractions were heated
under reflux in V U C Z ~ Ofor 1 hr., then distilled to give the
azine, b. p. 142"/12 inm., wDZ5 1.4584 (Found: C, 76.1;
H, 12-75; N, 11.3. C,,H,,X, requires C, 76.1; H , 12.8;
N, l l * l ? & v,),:,., (CC1,) 1635s c~ii.-l (sharp, single peak) ;
n.ni.r. (CC1,) : three complex signals centred a t I9-05, 8-53.,
and 7.76 in the intensity ratio 3 : 3 : 2 .
Reaction between the azinc (1 niol.) and anhydrous
hydmzine (50 inol.) or hydrazine hydrate (50 niol.) a t 90-
95" for 42 hr. in homogeneous solution (by addition of
n-propanol) gave products whose infrared spectra indicated
partial conversion into the hydrazone. The following
unsuccessful attempts t o convert the aziiie into the hydr-
azone were made : (i), azine (1 niol.) shaken for 2 days with
hydrazine hydrate (50 mol.), (ii), as (i) but for 16 hr. a t
90-95", and (iii), as (ii) but using anhydrous hydrazine.
4-Diazo-octane.-Calciuni oxide (1.2 g., 3 niol. ; recalcined)
and 12 drops of a saturated solution of potassium hydroxide
in dry ethFnol were added to octan-4-one hydrazone (1 g.,
1 mol.) in dry ether (12 ml.). With stirring a t O", yellow
mercuric oxide (4.56 g., 3 niol.) was added over 2 niin.,
and, with continued stirring a t 0", the course of the oxid-
ation was followed spectrometrically a t 500 nip
After an induction period (5-15 inin.), the concentration
of diazo-alkane rose to a ninximuni (60-80 inin.), then
slowly decreased. Filtration under gravity, arid removal
of the solvent a t 0" iqz Y ~ C U Ogave an effervescent, deep
pink oil (ca. 0.6 g.), v,~,,. (CC1,) 2050 cni.-l, which was
used as quickly as possible. The minimum purity, as
estimated from the percentage of products which could be
accounted for in its acetolysis,ls was 30-5504. Rapid
decomposition with evolution of nitrogen in carbon tetra-
chloride precluded the recording of a useful n.1n.r.
spectrum: after 90 inin., the solution had become colour-
less, and it then gave a spectrum consisting of 3 complex
signals at. ca. I9.0, 8.5, and 7.7 in thc ratio 3 : 3 : 2, but no
olvfinic protons were detected (d6.50,"). The colourless
solution had v ~ , 1720s ~ ~ . and 1635s cm.-l. Decomposition
of the neat liquid a t -78 to 0" was rapid (2-3 hr.) and
gave the same products. Traces of octenes (1.5-240,6)
were detected by gas ch:-omatography amongst the de-
composition products.
Yellow niercuric oxide which had be-eii dried a t 90" for
1 day was very inefficient in this oxidation.
One of us (K. 34. S.) thanks the D.S.I.H. for a niaiiiteiiancc
grant.
Uusor*l I'F-RRINSI~AEOKATORV,
OXFORDL 7 ~ ~ ~ ~ ~ ~ i ~ ~ ~ .
[:S,GlSS I I L C ~ I Z I .crptenzbfr
C~, 6th, 19651
l8 13. 31. Southain, D. Plul., Thesis, Oxford, 1965.