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Патент USA US2133037

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Patented 0cr.’11,193s
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’ ~' } METHODOF rRoDuciNG-nrmmm‘
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V ,Wendell:W.~_Moyer,‘
The. Solvay Process Company, New
WY”. York,
NI Y.,.
a corporation of New
" '
-l\To“Dra.wing.' Application January 3,1936," >
' ~
I "j
“ Serialv No.157,366ii'
" This invention relates to ‘aimethod for the ,amuneandpneimoi
I. .
-‘ '
in 300. molsof water,
preparation of diazo-amino compounds from‘ pri- ‘Imaintainedfat¢15° {C., 1.17» mols of . NOCl :were
mary amines.
passedi'atthe ratebftq??imol.penhour.‘ During
The invention has for its object the preparation
5 of diazo-amino compounds in a simpler, more
the-addition sthe: solutionewas. subJected to con
tinuous agitation to e?ect thorough admixture 01
e?icient, and more inexpensive manner than
and prevent localized overheating. Solid diazo
heretofore accomplished.
In the past diazo-amino compounds have been .
prepared from primary aromatic amines by ef-
10 fecting diazotizlng of the amine with sodium
nitritein acid solution, and treating the diazo
nium salt with an amine to produce the diazo- _ was formed as a precipitate during the reaction
amino compound.
> >
and; upon completion of the NOCl addition, was
In accordance With the Present invention I separated from the liquid by ?ltration. The solid
15 have found that primary aromatic amines may ' product thus obtained represented a yield of 80% _15
be reacted with nitrosyl chloride in the presence - based upon-the aniline employed. In lieu of NH:
of a base to give directly a high yield of diazo- any other suitable base ‘may be employed, for
amino product.
'instanceNaOH or NazCOa.
Any suitable base may be employed for the
20' purposes of the present invention. Thuaam-l
monia, sodium hydroxide. sodium carbonate, or
lime may be used satisfactorily. I have found
that an excess of the amine to be employed as
Example 2.-One mol of NOCl was added at
a now rateor 0.2 mol per hour with vigorous 20
striring to '7 mols of aniline maintained at 20° c.‘
In this’ case the excess aniline preserved the
alkalinity of the solution during the reaction.
the initial material may serve to advantage in
25 this Capacity Where a base other than the ~
amine is employed, the amine may be treated with
around half a mol of NOCl per mol of amine.
The amine may be dissolved in any suitable
solvent and the nitrosyl chloride may be passed
30 thereinto or the nitrosyl chloride and the amine
may be simultaneously introduced into the $01-vent. The amount .of base present should be
su?icient to maintain the solution neutral or
slightly alkaline during the reaction. The base
35 may be added entirely at the beginning of the
reaction or may be added gradually during the
addition of NOCl. Where theamine is employed]
as the base, it is of course necessary to increase
The - resulting mixture, which consisted of a
solution of diazo-amino-benzene and aniline hy- 25
drochloride in aniline, was then gradually warmed
to 40° to 50° C. and allowed to cool slowly to 20°
C..over a period of 17 hours. The yield of amino
azo-benzene was 86%, based on the N001 used.
The molar or formula ratio of nitrosyl chloride 30
to amine should not be in great excess of. one
to two as the excess NOClmay yield a diazonium
salt instead of the desired diazo-amino compound. ,
A ratio as .high as 1.3 to 2 may be employed,
however, without formation of asubstantial quan- 35
my of the diazonium salt. The ratio may be
much less than one to two as in the case .where
the amine is employed to bind hydrochloric acid,
the amount thereof so thatin additionto two‘ but whereranother base, say an inorganic'base,
40 mols of amine for each mol‘of NOClemployed, ;is employed ior'this purpose, it is desirable to 40
su?icient excess amine is. present to reform with employ‘an NOCI: amine ratio of at least 1/2.
liberated hydrochloric acidthe amine hydrochlo- _ The temperature of the reaction mixture is '
ride. This latter modi?cation of the invention, ' preferably maintained low, 1. e. is not allowed-to
wherein an excess of the amine is employed as rise substantially aboveabout 20° C., in order to
'45 the base, is especiallyapplicable to the prepara- ,. prevent premature rearrangement'and formation 45
tion of amino azo compounds since the diazoamino compound in admixture with the amine
of undesired by-products.
I claim: .
hydrochloride resulting from the treatment with
nitrosyl ChlOride may be converted to the corre50 sponding amino azo compound merely by, warm-
1. The method of preparing a diazo-amino
compound‘from a primary aromatic amine, which
comprises introducing NOCl into intimate con- 50
ing the mixture to a temperature around 40° C. ‘ tact with the arylamine in a formula ratio of
or higher.
not more than about 1.3 to 2v and maintaining
The following speci?c examples. will serve to ‘ su?icient base present to-bind hydrochloric acid '
illustrate the present invention:
Example 1.—-Into a solution of two molsot
formed during the reaction.
' 2. The method of preparing a dlazo-amino 55
compound from primary arylamine, which com
prises bringing nitrosyl chloride into intimate
contact with the amine in a formula ratio of
about 1/2 in the presence of sufficient ammonia
to react with the hydrochloric acid formed dur
ing the reaction.
3. The method of preparing ‘adiazo-amino
compound from a'primary arylamine,‘ which com
6'. The method of preparing an amino-azo
compound from a primary arylamine, which com
prises introducing NOCI pinto intimate contact
with the primary aryiamine at a temperaturenot
exceeding about 26° C. and maintaining su?icient 5
of the primary arylamine in excess of one mol
arylamine to TIA-{mol N001 to react with hydro
‘chloric acid formed during the reaction; and
a tem
, prises introducing about 1/2 mol of NOCl into a _ I
solution of a mol‘ of the primary arylaminerand ' ~ heatingthe resultant reaction'mixture to
perature above about 40° C.’
1/2 mol‘of ammonia at a temperature not in excess
of about 20° C.
~ 37. The method. of preparing diazo-amino-ben
fromaniline,’ which comprises introducing
4. The method of preparing a diazo-amino' _'zl_ene_,
about lpmol‘of NOCi into intimate contact with .
7 mols‘ of aniline at a temperature not ex
15 prises introducing NOCl into intimate contact; about
ceeding’abou't 20° C.
with‘ the primary aryiamine and maintaining suf-e
compound from a primary arylamine, which com.- '
' 8. 'The method of preparing amino-azo-ben
?cient' of the primary arylamine in excess of one
mol arylamine to 1/2 mol NOCI to react with» zenemfrom: anilineywhich comprises introducing
about 1 mol of NOCl into intimate contact with
hydrochloric acid formed during the reaction.’
. about ‘7 mols of aniline ‘at a temperature not
5. The'method or preparing a diazo-amino“
exceeding about 20° C'., and heating,r the resultant 20
.compound'from aprimary arylamine, which com
..prises introducing about .onemoi oi‘- VNOClv into :reactionfmixture toa temperature above about
iintimatecontactwith about fZmols of the primary ,
amineat a temperature not exceeding about 20°C.
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