Note: Descriptions are shown in the official language in which they were submitted.
~ ~ L
~ `
Tert-Octylhydrazine, It s Salts and Derivatives
. (IR 2744)
. .
Back~ound of the Inven~ion
Field of the Invention
5 This invention relates to ~ert-octylhydrazine (i.e.
~1,1,3,3-tetramethylbutylhydrazine), tert-octylhydrazine salts
and deri~atives of t-r~-occylhydrazine and, more '~1i`'
particularly, to che preparation of novel .
tert-octylhydrazones ! their hydrolysis to ~ert-octylhydrazine
salts, the neutralization of the salts ~o the free base
tert-octylhydrazine and the conversion of the free base to
other derivatives such as acid sal~s, hydrazones, hydrazides,
semicarbazides, carbazates or sulfonylhydrazides.
Prior Art
lS To the best of our knowledge tert-octylhydrazine (i.e.
1l1,3,3-tetramèthylbutylhydra7ine) has never been
successfully synthesized pr1or to this inveniton. Likewise,
none of its salts or derivatives have been reported.
~' ,'.
/-
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.. ,
Our U.S. Patent 4,604,455 entitled "Azoalkan~ Mixtures
Containing Unsymmetrical Azoalkanes, Their Method of
Preparation", discloses for the first time the
prepar~tion Oe unsymme~r~cal eer~-ocEyL.sec-al~yldiaZeneS.
S Ur~symmetrical eer~oc~yl cert-alkyldiazenes which are known
bu~ are incapable of isomerizing to ter~-oceyLhydrazones
(J. W. Timberlake, M. L. Hodges and .~. W.:Garner, Te~rahedron
Lett. p.3843, 197.3; J. W. Timberlake, J. Alender, ~
Garner, M. L. Hodges, C. Qz~e~al, S. Szilagyi, J. Org. Chem.
10 46, p.2082, 19~31). `
I~ is known in the literature ~ha~ sec-alkylazos can
isomerize co hydrazones upon heating. Co~Ley and Gipian
r~por~ted that secondary aralkyl azo compounds isomerize co
hydrazones in chlorinated solvents (R. Corley and M. Givian,
15 J. Org. Chem. 37, p. 2910, 1972).
Statement of the Inven~ion
This invention relates ~o tert-octylhydrazine (I), a
IH3 1 3
CH3-c-cH2-l-NH NH2
CH3 CH3
266~84
~ .
~.
C'
novel mono-subs~ituted s~erically hindered tert-alkylhydrazine.
Due to the bulky tert-octyl substitutent, it was not possible -
to synthesize this compound by the conventional techni~ues
and consequently it has not been prepared prior to this
.5 invention. --
This invention, also, relates to the novel acid salts oftert-octylhydrazine of the general formula 11.
C~3 CH3
3 I CH2-CI-NH NH2 A
.. _ CH3 CX3 ~ n '.: r~
where n = 1 or 2; when n is 1, A is selected from HCl, HBr,
H2SO4~ H3PO4~ -
O ; O O
Il 11 11
RCOH or HOC-COH where R is selected from H, CH3, C2HS,
20~ C3H7, i-C3H7, and C6H5; and when n is 2, A is selected from
one of the following
O O O O
Il 11 11 11
H2SO4, HOC-COH or HOCCH2CH2COH.
This invention also is directed to the novel tert-
octylhydrazones of the general formula T IIo _
CIH3 IH3 R
CH3-C-CH2-C-NH-N=C-R2
CH3 CH3
.
- 4 ~ i~
~,
.
. ~.
- where Rl and R2 are independently selected from alkyl or i:
;~ ..
substituted alkyl of 1-12 carbons, preferably 1-6 carbons, . :.~
r~
cycloaliphatic of 3-12 carbons, preferably 3-7 carbons, or
to~ether can form an alkylene diradical of 3-11 carbons,
preferably.4-7 carbons and Rl can also be hydrogen and R2
can also be phenyl or substituted phenyl of 6-14 carbons,
preferably 6-10 carbons.
The invention also comprehends the novel derivatives of
tert-octylhydrazine of general structure IV and V
. IH3 CIH3
3-c-cH2-c-NH-NH-y
`~ CH3 CH3
~V
_ ~ .
.~ IC~3 IH3
CH3 -C-CH2-C-~H-~IH Z ~:
_ H3 CH3 ' ~ 2
V
O O O R4 0
where Y is selected from -COR3, CR3, -C- ~ , or-S-R3
~2~;6~
O O O O O R R O
~ 14 14 11
and Z is selected from -COR60C-, -C-R6-C-, -C-N-R6-N--C-,
O o
Il 11
or -S-R -S
Il 7 ll
O O
R3 is selected from an alkyl of 1-12 carbons, an aryl or
substituted ary-l of 6-14 carbons, a cycloalkyl of 3-8
carbons, or an aralkyl of 7-9 carbons;
R4 and R5 are independently selected from hydrogen, an alkyl
of 1-12 carbons, an aryl or substituted aryl of 6-14 carbons,
an aralkyl of 7-9 carbons, a cycloalkyl of 3-8 carbons, or
together can form an alkylene biradical of 4 to 7 carbons;
R6 is selected from an alkyl of 1-12 carbons, a cycloalkyl of
3-10 carbons, an alkylcycloalkylalkyl of 6-14 carbons or an
aryl of 6-14 carbons, an alkylaralkyl or aralkylaryl
diradical of 8-15 carbons and R6 may optionally contain ether
linkages in the backbone; and
R7 is biphenylene.
Detailed Description of the Invention
Tert-octylhydrazine tl), a unique mono-substituted
sterically hindered test-alkylhydrazine, is a very useful
intermediate for preparing low temperature azo compounds.
;~ '
~L26~
-- 6 --
The tert-octyl group has a marked effect on lowering the
half-life of azoalkanes and unsymmetrical azonitriles.
U.S. Patent 4,604,455 discloses a two step preparation
of a mixture of unsymmetrical and symmetrical diazenes
by first reacting at least two primary alkyl-, cycloalkyl-,
or aralkylamines with sulfuryl chloride in the presence
of an anhydrous-inert solvent until the mixture of the
N,N'-disubstituted sulfamide product is formed. The amine
hydrochloride byproducts are removed by an aqueous wash
and the mixture of sulfamides are oxidized with basic
bleach in a strongly basic medium to form the mixture of
diazenes. If a low molecular weight secondary alkyl
primary amine, such as isopropylamine, is used in conjunction
with the tert-octylamine in this process, the low boiling
symmetrical diazene is evaporated during the work up and a
mixture of di-tert-octyldiazene and the unsymmetrical diazene
remains with the unsymmetrical diazene being the major
component. These unsymmetrical tert-octyl sec-alkyl (or
primary alkyl) diazenes are also novel compounds.
The mixture of diazenes is heated in a chlorinated
solvent, such as chlorobenzene, dichlorobenzene, or
trichlorobenzene, at 120-150C. The di-tert-octyldiazene
decomposes to liberate nitrogen, diisobutylene, and
diisobutane Unexpectedly, the tert-octyl sec-al~yl (or
;4B4
primary alkyl) diazene rearranges to a tert-octylhydrazone
instead of decomposing. If there is any of the symmetrical
secondary (or primary) azoalkane present, it will also
rearrange to a hydrazone. Therefore, it is preferable to use
a low molecular weight amine such as isopropylamine in the
sulfamide reaction to eliminate this problem.
The unsymmetrical diazene rearr,anges readily (1-2 hours)
to the extent of about 80-90%.
The tert-octylhydrazone can be extracted out of the
chlorobenzene solution with dilute sulfuric acid. The
tert-octylhydrazone forms the sulfuric acid salt which is
water soluble, The tert-octylhydrazone can be partially
extracted out of the chlorobenzene solution with hydrochloric
acid. The tert-octylhydrazone forms the hydrochloride but
the hydrochloride is soluble in the chlorobenzene solution
and only partially goes into the aqueous layer. Therefore,
it is advantageous to extract the tert-octylhydrazone out of
the chlorobenzene layer with dilute sulfuric acid. The
di-tert-octyldiazene decomposition produc-ts and the
unrearranged diazene remain in the chlorobenzene layer. The
chlorobenzene layer is separated and can be recharged with
fresh diazene mixture and the rearrangement repeated.
Upon neutralization of the sulfuric acid solution, the
tert-octylhydrazone is obtained. Usually a small amount of
hydrolysis occurs and the tert-octylhydrazone is contaminated
L2~;G484 ~
~ ` .
';
~.
with some tert-octylhydrazine and the corresponding ketone.
If the mixture is refl~Yed, the free tert-octylhydrazine will
react with the ketone to reform the tert-octylhydrazone.
If the sulfuric acid solution is heated, the ketone that
forms is remQved by dis~illation, pre~erably under reduced
pressure; the ter~-octylhydrazone will hydrolyze completely
to an aqueous solution of tert-octylhyrazine sulfate.
The pure salt can be obtained by evaporation of the
water. The hydrolysis is preerably c~rried out under
~0 reduced pressure to prevent dealkylation of the
tert-octylhydrazine and formation of hydrazine sulfa~e. The
hydrolysi`s of tert-octylhydrazone hydrochlorides can be
carried out in similar fashion.
~he tert-octylhydrazine salt solution can be neutralized
with an inorganic base, such as sodium or potassium
hydroxides, carbonates, or bicarbonates, to form the free
tert-octylhydrazine. ter~-Octylhydrazine has poor water
soLubility and separates out of solution as an organic layer.
It c-an be taken up in hydrocarbon solvents, such as pentane
or hexane~ dried, and heated to evaporate off the soIvent.,
tert-~ctylhydrazine has a very obnoxious and pungent
odor so it is advisable to store it as an acid salt. The
free base is probably more toxic than the acid salts so that
care should be e~ercised when handling the free
tert-octylhydraz:ine.
Z~i~lB4
. -:
-;
~'-
If the diazene mi~ture con~ained any of the cymmetrical
di-sec-alkyl ~or primary alkyl) diazenes and it was not ;-
removed before heating the diazene solution in the
chlorinated solvent, the tert-octylhydrazone would be
contaminated wi-th the corresponding sec-alkyl (or primary
alkyl~ hydrazone and the tert-octylhydrazine would be :
contaminated with some o the corresponding primary secondary
alkylhydrazine. This is not a problem when isopropylamine is
used with t-octylamine in the sulfamide reaction.
~0 tert-Octylhydrazine is-useful as an intermediate for low ~-
temperature azo compounds such as 2-tert-octylazo-2-cyano-
.. ~.,
propane,`as an antioxidant, as an antiozonant, and as a ~
1~,,,,7/,,.,U',-,~'
pharmaceutical intermediate. '! , .'
-~he acid salts of tert-octylhydrazine (II) are readily
lS prepared by reacting tert-octylhydrazine with an equi-molar
amount of the desirèd acid. This can be done in aqueous
solutions, and, in most cases, an aqueous solution of the
salt will result. The acid can also be added to a
hydrocarbon solution of tert-octylhydrazine and the
hydrocarbon, preferably pentane or hexane stripped off to
leave the salt. The hydrochloride or sulfate salts can also :
be prepared by reacting tert-octylhydrazones with an
equi-molar amount of the acid and by stripping off the ketone
that forms as described earlier. ~-
In addition to being convenient forms of storing the
oxygen sensitive tert-octylhydrazine, the salts are efficient
,`.
~L2~;6~
1 0
, ". `.
L; '
foaming agents or polyester resins according to the method :--
described by ~amens (U.S. Patent 4,393,148). -
The tert-octylhydrazones (III) are generally prepared by
reacting tert-octylhydrazine (I) with a ketone or aldehyde.
S With most aliphatic ketones and aldehydes, the reactlon is -
usually carried out by neutralizinG an aqueous solution of
tert-octylhydrazine sulfate (or hydrochloride), adding an
equi-molar amount of the ketone or aldehyde, and refl~Ying
the a~ueous mi~ture for about an hour. The ex~ent of
I0 reaction can be foIlowed by gas chromatography. In the case
of less reactive ketones, such as acetophenone, it is
desirable to run the reaction in an inert solvent such as
toluene and drive the reaction by azeotroping off the water
that orms. The reaction can be catalyzed by adding a small
amount of para-toluenensulfonic acid.
The tert-octylhydrazones (III) (Rl is not H and R2 is
not C6H5) are useful in the synthesis of low temperature azo
compounds. Hydrocyanic acid can be added across the double
bond and the resulting hydrazonitrile oxidized to the
corresponding a~onitrile.
The tert-octylhydrazides (IV) and (V) can be prepared by
reacting tert-octylhydrazine with acid chlorides or diacid
chlorides in~the presence of an acid acceptor. These ~
compounds are useful as blowing agents. They may be oxidized ~;
25 to the corresponding azo compounds which are useful as ~
.,
. ~
~ ~.
blowing agents and as initiators for the polymerization of
vinyl monomers.
The tert-octyl substituted carbazates can be prepared by
reacting tert-octylhydrazine with chloroformates or bis
chloroformates in the presence of an acid accepter. These
compounds are also useful as blowing agents. ~hey may be
oxidized to ehe correspondin! azo esters which are useful as
blowing agents and as initia~ors for the polymerization of
vinyl monomers.
The substituted tert-octyl semicarbazides can be
prepared by reacting tert-octylhydrazine with alkali metal
cyanatesj isocyanates, diisocyana~-s, or substituted ureas.
These compounds are also useflll as blowing agents. They
may b~e oxidized to the corresponding azo amides which are
useful as blowing agents and as initiators for the
polymerization of vinyl monomers. ~
The substituted tert-octyl sulfonylhydrazides and bis
sulfonylhydrazides can be prepared by reacting
tert-octylhydrazine with sulfonyl chlorides or disulfonyl
chlorides in the presence of an acid acceptor. These
compounds are also useful as blowing agents and as foaming
agents for unsaturated polyester resins.
, ~
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Example I ~
Preparation of Cyclohe~yl t:ert-Octylidiazene ,
,,
Into a 1 liter 3-neck flask were added 40.8 grams (0.3
mole) of 95% tert-octylamine, 33.9 grams (0.325 mole) of
cyclohe.xylamine and 300 ml of he~ane. The flask was
equipped with a magnetic stirrer, thermometer, and Dean
Stark trap connected to a reflu~ condenser. The flask was
lowered into an 80C preheated oil bath and the he~ane
solution was refl~Yed using the Dean Stark trap to remove
water which was azeotroped cEf ~i~h ~exane rom t~e reac~ion
mass for~I/2 hour. The water tha~ formed in the trap was i~`
separated and the he~ane layer added back to the reaction
-flas~. The magnetic stirrer was replaced with a mechanical
stirrer and the flask was equipped with a 25 ml dropping
lS funnel, air condenser, and thermometer. ~he he~ane solution
of the dried amine was cooled to 0C and 20.9 grams (0.15
mole) or 97% sulfuryl chloride was added dropwise from the
dropping funnel over 20-30 minutes while holding the
temperature below 15C. After the addition was completed,
the reaction was warmed to 30C and stirred 1/2 hour at
Z5-30'C. The reaction was diluted with water ~o dissolve
v, ~
. .
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,.~
. .
the hydrochloride salts and transferred tO a separatory
funnel. The aqueous layer was separated and the he~ane
,
layer was washed with I00 ml of 10% H2SO4 to remove any
residual amine. The acid wash was separated and added to
the aqueous layer for neutralization and recovery of amine.
The he~ane layer was transferred back to the 1-liter
3-neck flask and 0.5 grams of .~dogen 464 (a trademark to
cover methyltrialkyl (C~-C10) ammonium chloride, marketed bv
Aldrich Chemical Company) phase transfer catalyst and a
solution of 40 grams (0.5 mole) of 50% sodium hydro~ide in
250 grams of 14.2% bleach were added. The flask was
equipped~with a ma~netic stirrer, thermometer, and 5~;-
distillina head connected to a condenser and receiver. The
flask~was lowered into a preheated oil bath (~80C) and
stirred viaorously ~ich the magnetic s~irrer. When the
reaction mi~ture warmed up to 62C, the h~a~e began co
distill, and o~idation began to occur. Ogidation was
essentially completed by the time distillation ceased. The
reaction mixture was stirred an additional hour at 85C
before cooling back to room temperature. The reaction
mixture was diluted with 100 ml of hexane and transferred to
a separatory funnel. The aqueous bleach layer was separated
. - o ~6~ ~ ''
- 14 -
,..
and the hexane solution of the di.azenes was washed
successively wi~h 100 ml poritions of water, 15% sodlum
bisulfite solution, 10% H2SO4, and saturated sodium
bicarbonate solution. The hexane solution was dried over
S anhydrous sodium.sulfate, filtered, and heated ~o strip off ~.
the solvent on a rotary evaporator under reduced pressure.
The residue weighed 29,1 grams and was composed of
approximately- 20% of di-ter~-oc~yldiazene, 12% of
dicyclohe~yldiazene, and 65% of the de.sired cyclohexyl
tert-octyldiazene.
- Subsequent runs were carried out wh-re the mole ratio
of the cy-clohe.~ylamine and tert-ocrylamine were varied
slightly. The results were summari7ed in ~he following
Table. I
~3 iai~6~1~
-- .
Z o ~ ~,
Z
-
. .
-
;
,
In ,~, z ,n ~, c~
l O 1
.-,~
. I C3 ~O ~ CS~
-- .
;~1 = ~ `* U~
I C '
.
. ~ O
~ .
C
l~a~ ~
- 16 -
~.
E.Yample II
Preparation of Isopropyl tert-Octyldiazene
Several runs of isopropyl tert-octyldiazene were made
using the procedure described in E~mple I but substituting
isopropylamine for cyclohe~ylamine. The crude product was
primarily a mi~ture of di-tert-octyldiazene and isopropyl
tert-octyldiazene. This product did not contain any
diisopropyldiazene. The reaction was run on a larger scale
in a 2 liter 3-neck fIask employing 1.3 moles of
isopropyl~amine, 1.2 moles of tert-octylamine, 0.6 mole
sulfuryl chloride, 800 ml of he~ane, 1 ~ram of Adogen 464,
and a soIl?tion of 300 grams of 50% sodium hydroxide in 1200
grams of 12% bleach. The product after workup weighed 66
grams and was composed of appro~imately 6S~/o isopropyl
tert-octyldiazene and 25% di-tert-octyldiazene.
Example III
Preparation of Cyclohe~anone tert-Octylhydrazone and
tert-OctylhYdrazine Hvdrochloride
~ = . ~ . .
A mixture of di-tert-octyldiazene (32.5%),
dicyclohexyldi.azene (9%) and cyclohe~yl tert octyldiazene
(53%) weighing 27.6 grams was diluted with 83 grams of
o-dichlorobenz:ene and added to a 3-neck 250 ml round bottom
flask. The flask was equipped with a magnetic stirring bar,
.
refl~Y condenser, and nitrogen purge. The solu~ion was
heated for 3~ hours at 120-125C. Gas chromatographic
analysis indicated that about 75% of the cyclohe~yl
tert-octyldia7ene had rearranged to cyclohe~anone
S tert-octylhydrazone. The re~ction was cooled to room
temperature and ~he dichlorobenzene solution e~tracted with
50 ml of 5% HCl. The acid e~tract was set as-ide and the
diclorobenzene solucion recharged with an additional lS grams
of diazene mi~ture and the solution heated ~or 2 hours at
}0 120-130C. Gas chromatographic analysis indicated the
cyclohe~yl tert-octyldiazene had rearranged about 70% to the
hydrazone. The soIution was cooled to room temperature and
extracted with another 50 ml of 5% HCl. The acid e~tract was
added to the first extract and the dichlorobenezene solution
recharged with an additional 14.4 grams of the diazene
mixture. The dichlorobenzene had rearran~ed about 70% to
cyclohexanone tert-octylhydrazone. The dichlorobenzene
solution was heated for 2 hours at 120-125C and cooled back
to room temperature. Gas chromatographic analysis indicated
that the cyclohexyl tert-octyldiazene had rearranged about
70% to cyclohexanone tert^octylhydrazone. The
dichlorobenzene solution was extracted with another 50 ml of
5% HCl and the acid eætracts were combined. The acid
extracts were washed twice with pentane to remove any
residual dichlorobenzene. The acid was then neutralized with
60 ml of 10% NaOH and extracted twice with 5Q ml of pentane.
- 18 -
The pentane extracts were combined and analyzed by gas
chromatography. The pentane solution contained a mixture of
tert-octylhydrazine (~75~) and cyclohexanone tert-octyl-
hydrazone (~20%).
Since the hydrolysis of the hydrazone was incomplete,
the pentane solution was treated with 10% HCl (30ml) until a
pH of 0.5 was obtained. The aqueous solution was separated
and allowed to stand overnight. Pure tert-octylhydrazine
hydrochloride was obtained by stripping the solution to
dryness and recrystallizing the residue from ethanol. The
recrystallized hydrochloride was a white crystalline solid
which melted at 141-143C with gassing.
Neutralization of the dichlorobenzene solution with
sodium bicarbonate solution generated a considerable amount
of cyclohexanone t-octylhydrazone indicating that
cyclohexanone t-octylhydrazone hydrochloride is quite soluble
in dichlorobenzene and is not extracted out of the
dichlorobenzene very efficiently with water. The residual
cyclohexanone tert-octylhydrazone was efficiently extracted
out of the dichlorobenzene with dilute sulfuric acid.
~5L2~
~ . .
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E~ample :[V ~-
Preparation of Acetone tert-Octylhydrazone and
ter~-Octylhydrazine Sulfate
A mixture of di-tert-octyldia~ene (27%) and isopropyl
S tert-octyldiazene (65%) weightin~ 33.5 grams was dilu~ed with ~-
67 grams of chlorobenzene and added to a 3-neck 250 ml round
bottom flask. The flask was equipped-with a magnetic
stirring bar and refl~Y condenser and was purged with a
steady stream of nitrogen. The solution was gently refl~Yed
lO for 3 hours at 134C and then cooled below 20C. Gas !~
-chromacographic analysis indicated that the isopropyl
tert-oct~ldiazene had rearranged about 88% to acetone
tert-octylhydra20ne. The reaction mi~ture was dilu~ed with
75 ml~of water; 20 grams of 70% H2S04 were added dropwise.
The mi~ture was stirred vigorously for 5 minutes and
transferred to a separatory funneL. The 'aqueous layer was
separated and the chlorobenzene layer was washed with an
additional 25 ml of water; ~he aqueous wash was added to the
acid layer. Neutralization of a small sample of the
2Q chlorobenzene layer indicated the absence of any acetone
tert-octylhydrazone indicating that it had all been e~tracted
into the acid layer. The acid layer was washed with 50 ml of
hexane to remove any residual ch}orobenzene. Neutralization
of a small sample of the acid layer indicated that 60% of the
acetone tert-octylhydrazone had hydrolyzed to tert-octyl-
hydrazine.
o ~3L2e;~
- 20 -
,
, .
The aqueous acid solution weighed 141 grams. It was
then stripped for 1~ hours on a rotary evaporator at 30-40C
under reduced pressure. The final aqueous solucion weighed
62.8 grams and contained Z4.9% tert-octylhydrazine
(iodometric titration) which was present as ~he sulfa~e.
~eutralization of a small sample of the acid solution
indicated the presence of a small amount (~5%) of
unhydrolyzed acetone tert-octylhydrazone in the
tert-octylhydrazine.
..
E~ampL~
` Preparation o~ t -OC ~yi:nvd~azine 1`
.
- ~ mi~ture of di-tert-octvld~aze~e (~') and isopropyl
tert-octyldiazene (~2h) weighin~ ~7.2 arams was diluted with
65 grams of chlorobenzene and refl~ed for 3 hours at 134C
as in ~Yample IV. The reaction mixture was cooled to 20C
and diluted with 100 ml of water; 14 grams of 70% H2SO4 was
added dropwise. The aqueou~ layer was worked up as in
Example IV and then stripped for 1 hour at 30-40C on a
rotary evaporator under reduced pressure. This solution of
tert-octylhydrazine sulfate weighed 35.2 grams. A small
sample was made basic and e~tracted with hexane. A VPC scan
of the e~Ytract indicated that the hydrolysis was completed.
The aqueous solution was diluted with 100 ml of water
and made strongly basic by the addition of 24 grams of 50%
2~
` - 21 -
.
,
~aOH. The mi~ture was cooled to 20C and e~tracted with 100 ~
ml of pentane. The pentane e~tract was dried over anhydrous
sodium sulfate, filtered, and heated to strip of the
pentane. The residue was a yellow liquid which wei~hed 11.0
grams. Gas chromatographic analysis indicated that the
product was approximately 85% tert-octylhydrazine. .~ttemp~s
to vacuum distill the product led to gassing and slow
decomposition around 50C.
~Yample VI ~
10Pre~aration of Methyl Ethyl Ketone tert-Oc~vlhvdrazone '`
.,
.. , , ,~
rO a solution fo 24.2 grams (0.10 mole) of ter~-octyl-
hydra~ine sulfate ~prepared as in E~ample IV) in 48.3 grams
of water in a 3^neck 250 ml round bottom flask, were added 25
ml of water, 8.6 grams of methyl ethyl ke~one, and 20 grams
of 50% sodium hydro~ide. The flask was equipped with a
magnetic stirrer~ thermometer, and refluY condenser and was
heated in an oil bath. The reaction mi~ture was refluYed
gently for 1 hour, cooled to 60C, ànd transferred to a
separatory funnel. ~he aqueous layer was drained off from
the organic layer; the organic layer was then diluted with 50
ml of hexane, dried over anhydrous Na2SO4, filtered, and
heated to strip off the solvent on a rotary evaporator at
30C under reduced pressure. The crude product weighed 17.5
grams and assayed about ~0% by gas chromatographic analysis.
` ~ - 22 - ~ ' '
. . .
~ , .
The corrected yield of methyl ethyl kecone
tert-octylhydrazone was appro~imately 80%. There was no
methyl ethyl ketone ketazine present indicating that the
tert-octylhydra~ine sulfate was not contaminated with any
hydrazine sulfate.
E.Yample VII
Preparation of the Oxalic .~cid Salt of tert-Octvlhydrazine
To a solution of 5,grams of o~alic acid dihydrate in 15
ml of ethanol and 20 ml of e~her were added 5 gram,s of methyl
ethyl ketone tert-octylhydrazone. The mi~Yture was stirred
for 1 hour at room temperature. A white precipitate began to
form ,after 10 minutes. After the hour stirring period, the
white solid was filtered off, washed with 5 ml of ethanol,
, pulled semi-dry on the filter, and air dr'ied on a tared watch
glass. The product weighed 2.2 grams and had a melting point
of 128-130C.
A second crop of 1.0 gram was obtained by concentrating
the filtrate and refiltering it~
The filter cake was slurried in water, neutralized with
caustic, and e~tracted with hexane. The hexane e~tract was
dried over ~a2SO4, filtered, and heated to strip off the
hexane on a rotary evaporator under reduced pressure. The
residue weighed 1.0 gram and was identified as tert-octyl-
hydrazine by gas chromatographic retention time.~
~ .
''~
E~ample VIII ,-
Preparation of l-~ert-Octyl-2-etho~ycarbonylhydrazine
To 62 grams of a solution containing 3.84 grams (O.026
mole) of tert-octylhydrazine (as ~he sulfate) was added
5enough 50% NaO~ (6.3 grams) to bring the pH up to 9. Then 5
grams of sodium carbonate were added and the mi~ture cooled
~o 10C. The tert-octylhydrazine separated out of solution
and 25 ml of he~ane were added. The mi~ture was stirred and
a solution of 2.8 grams (0.026 mole) of ethyl chlorofomate in
5 ml of he~ane was added dropwise over L hour whi~e holding
the tempèrature at 10-15C. Ihe addition was monitored by
gas chromatography; when about 80% of the chloroformate
-solution had been added, it appea~red that all the
tert-octylhydrazine had been consumed. Therefore, the
addition was stopped to prevent diacylation. The reaction
mixture was transferred to a separating funnel and the
aqueous layer was separated. The-he~ane solution was washed
with saturated sodium bicarbonate solution and water, dried
over anhydrous sodium sulfate, filtered, and heated to strip
off the he~ane on a ro~ary evaporator under reduced pressure.
The residue was a light yellow liquid weighing 3.7 grams.
The infrared spectrum of the residue had a strong broad l~H
peak at 3315 cm 1 and a very strong broad carbonyl peak a~
1710 cm~l.
24 ~ ,
. ' - ` - .
~.;
The product was oxidized~to the corresponding aZG ester
with 30 grams of 12% bleach. The product weighed 3.8 grams
and was 93% pure by gas chromatographic analysis. The
infrared spectrum of the oxidized product did not contain any
peaks in the NH region (3200-330Q cm 1) and the carbonyl peak -
was very sharp and shifted to 1770 cm 1, The azoester was an
orange liquid and gassed moderately from 1~0C tO 180C and
rapidly above 180C. It would be useful as a blowing agent
for vinyl resins.
': _ t~"' `
~ample I~
- f,~
`~ Preparation of l-ter~-Oc~ylsæmicar'?azide ~
..
- Into a 125 ml erlenmeyer flask were weiched 20.9 grams
of a solution which contained 5.2 grams (0.036 mole) of ter~-
octylhydrazine as- the sulfate. .~ magnetic stirring bar was
added and the so~ution was partially neutralized by adding
3.25 grams (0.04 mole) of 50%.sodium hydroxide. ~ solution
of 5.24 grams (0.065 mole) of potassium cyanate in 20 ml of
water was slowly added over 15 minutes while holding the
temperature between 20C and 25C. A~ter the addition was
completed, the reaction mixture was stirred one hour and the
solids that formed was fil~ered off. The filter cake was
washed with pentane and air dried. The dried filter cake
weighed 3.7 grams and had a meIting point of 176-178C.
'.
- 25 -
A second crop of product was obtainea by recharging the
aqueous filtrate with 2 grams of potassium cyanate and
stirring the mixture an additional hour. The solids that
formed were filtered off and air dried. The second crop
weighed 2.2 grams and had a melting point of 175-177C. The
infrared spectrum of the product contained MH bands a-t 3200
cm 1, 3250 cm 1, and 3450 cm 1 and a strong carbonyl band at
1660 cm and an amide II band a~ 1580 cm
The l-tert-octylsemicarbazide was oxidized to tert-
octylazoformamide with neutral permanganate in 22% yield. The
tert-octylazoformamide was a yellow crystalline solid which
melted at 63-64C. It began gassing at 110-120 C and gassed
rapidly above 130C.
Example X
Preparation of l-tert-Octyl-2-para-toluenesulfonylhydrazine
Into a 3-neck 250 ml flask were weighed 20.9 grams of a
solution which contained 5.2 grams (0.036 mole) of tert-
octylhydrazine as the sulfate. The solution was diluted with
50 ml of water; 28.8 grams t0.072 mole) of 10~ sodium
hydroxide and 10.6 grams (0.1 mole) of sodium carbonate were
then added. The flask was equipped with a magnetic stirring
bar, thermometer, and dropping funnel and was placed in a
cold water bath. In the meantime, 7.6 grams of para-
toluenesulfonyl chloride were dissolved in 50 ml of toluene
~7
.æ~
26 -
and added to the dropping funnel. The toluene solution was
added to the rapidly stirred aqueous solution while holding
the temperature at 15-20C. The addition required 15 minutes
and the reaction mass was stirred an additional hour after
- S the addition was over. White soli.ds formed during the
addition period. At the end of the stirring period, the
reaction migture was filtered and the filter cake was stirred
in he~ane, refiltered, and air dried. The whit~. powder
weighed 7.3 grams. The product decomposed with rapid gassing
upon melting at 108-110C. L
!
E~ample ~I
Preparation of l-tert-Octyl -2-meta-chlorobenzoylhydrazine
Into a 3-neck 250 ml flask were weighed 18.0 grams of a
solution which contained 4.9 grams (0.03 mole) of tert-
octylhydrazine as the sulfate. The solution was diluted with50 ml of water; then 6.2 grams (0.078 mole) of 50% sodium
hydroxide were added to raise the pH to 9 and then 4.24 grams
(0.04 mole) of sodium carbonate were added. The flask was
equipped with a magnetic stirring bar, a thermometer, and a
~0 dropping funnel containing 4.9 grams (-0.03 mole) of meta-
chlorobenzoyl chloride. The reaction mixture was diluted
with 25 ml of hexane and then with rapid stirring the meta-
chlorobenzoyl chloride was added dropwise over 10 minutes
while holding the temperature between 18 and 25C. After the
- 27 -
addition was completed, the reaction was stirred an
additional 30 minutes and the white solid that formed was
filtered off. The filter cake was slurried in a mixture of
100 ml of hexane and 100 ml of warm water and refiltered.
The filter cake was pulled semi-dry on the filter and then
air dried to constant weight. The product was a white powder
that weighed 7.3 grams and had a melting point of 133-137C.
The infrared spectrum of the product had a s-trong NH band at
3200 cm 1 and a StrOilg sharp carbonyl band at 1620 cm 1
Example XII
Preparation of Terephthaloylbis(2-tert-octylhydrazide)
Into a 125 ml erlenmeyer flask were weighed 3 grams of
85~ tert-octylhydrazine, 20 grams of water, and 2.1 grams of
sodium carbonate. The flask was equipped with a magnetic
stirring bar and thermometer; 25 ml of ether was then added.
The mixture was stirred rapidly and a solution of 1.8 grams
of terephthaloyl chloride in 25 ml of ether was added
dropwise while holding the temperature between 25-30C.
White solids formed immediately upon adding the ether
solution. The reaction mixture was stirred an additional 1/2
hour and filtered. The filter cake was rinsed with
additional ether, reslurried in warm water, and refiltered.
The filter cake was pulled semi-dry on the filter and air
dried to constant weight on a tared watch glass. The dried
i3 Q
~- - 28 -
product weighed 3.5 grams and melted at 242-245C with
decomposition. The infrared spec:trum had NH bands at 3240
and 3280 cm 1 and a sharp carbonyl band at 1630 cm 1.
- - Example XIII
Prepration of 1,13-Di tert-octyl-1,2,12,13--tetraazo-3,11-
dioxo-4,7,10-trioxo-tridecane
Into a 135 ml erlenméyer flask were weighed 4 grams of
85% tert-octylhydrazine, 20 grams of water, and 2.65 grams of
sodium carbonate. The flask was equipped with a magnetic
stirring bar and thermometer; 25 ml of hexane was then added.
The mixture was stirred rapidly and 2.65 grams of diethylene
glycol bis chloroformate were added dropwise while holding
the reaction temperature between 20 and 30C with a cold
water bath. After the addition was completed, the reaction
mixture was stirred an additional hour a~ room temperature.
A gas chromatographic scan indicated that all of the tert-
octylhydrazine had reacted. The mixture was transferred to a
separatory funnel and the aqueous layer was separated. The
hexane layer was washed with 25 ml saturated sodium
bicarbonate solution, dried over anhydrous sodium sulfate,
filtered, and heated to strip off the hexane on a rotary
evaporator ~mder reduced pressure. The residue was a light
yellow liquid weighing 5.5 grams. The infrared spectrum of
- 29 -
~he produc~ h~d ~ ~trong ~road NH b~nd a~ 3300 cm and a
s~rong broad carbonyl band a~ 1700 cm 1,
The bis hydrazo ester was oxidized eo che corresponding
bis azoester by stirring a met~lylene chloride solu~io~ o~ ~he
.5 hydrazo ester wich 50 grams o~ bleach for about 4 hours. The
;. methylene chloride solution of ~he azoescer was washed wi~h
saturated sodium bicarbonate ar~d water, dried over anhydrous
sodium sulfaee, filcered, and heated eo s~rip o~f the
methylene chloride on a rotary evaporaeor under reduced
pressure. The residue was a dark yellow-orange liquid
weighing 4.7 grams. The infrared spec~rum of the-azoes~er.
showed che absence of any .~H bands and ~he carbonyl band was
, sharp and shif~ed ~o 1760 cm~l. The azoester gassed mildly
; from 140-150C, moderately from 150-165C, and rapLdly above
0C.
ample ~IV
~oaming an Unsa~uraced Polyescer Resin with
Tert-Octylhydrazine Derivacives
The unsacurated polyes~er resin was Laminac 4123*(an
orthophchalic acid-based resin concaining approximacely 30%
; scyrene monomer, markeced by U.S.S. Chemicals). The resin
was modified by adding an addicional 5 phr scyrene monomer
and 1 phr Dow Corning 193* surfactant.
The resin and all ocher componencs e~cepc che pero~ide
cacalysc were weighed inco 9-ounce wa~ed paper cups and
* trade mark
~4~
~ - 30 -
~ , .
blended using a high shear electric miYer. The pero~ide
catalyst was then added and blended in; at this time an
electric timer was activated in order to obtain gel times
(time to peak foaming). ~fter mi~ing at high shear for about
- 5 10 seconds, 3Q gram portions of the ml~tures were poured into
3-ounce paper cups and allowed to foam. Gel ~imes and foam
densities were determined from these samples. Densities wer-
determined by the water displacement method. The results are
summarized in the following Table II.
~he cured but unfoamed Laminac 4123 resin has a density
greater than 70 lbs./cu.f~
j..
- 31 -
Table II
~oaming an Unsaturated Polyester Resin
tert-Octylhydrazine .~ert C8H17 NH2 HCl ~Y# ~ ~# ~1
Derivative (ExamPle#)
5Parts derivatrve/hundred parts 0.86 1.45 1.3
. resin
phr 45% FeC13 0,4 0 4
phr 6% Cobale Neodecanoate 0-05 0.1 0.3
phr S% Copper Naphthenate ~ 4
phr Lupersol Delta ~-9~ 3.0 3.0 3.0
g~l cime in minuces 2.0 2.0 3.0
:,. ;
density lbs./cu. ft. 33 41 41 ~.
* Trade mark for a commercial formulation of Methyl Ethyl ~ :
Xetone Peroxide and Hydrogen Peroxide in D~methyl Phthalate` -
Lucidol Division of Pennwalt.
9~
