вход по аккаунту


Патент USA US2406504

код для вставки
Patented Aug. 27,‘ 1946 ‘
NITRO KETALS m ‘teams Fort’
Glen II. ‘Morey, Terre Haute, Ind}, assignor to
Ilaute,_Ind., a corporation of Maryland; }
No Drawing. Application ‘at ‘29, 19.44,? p "1
Serial No. 547,283 g
8 Claims. (01. 260-338) ‘
The present invention’ relates to a‘series of new‘
ketals and to a process for-,theirlpreparation.
More particularly it pertains to ketals haVingJdi
effected between any alkyl levulinate ‘and’ any 2- ‘
nitro-‘l_,.37propanediol. ,
The acid‘ catalyst utilized in producing the new
versiiled'~v functional I groups. '1 ‘Speci?cally, such
I ketals of my invention may be selected froma rel
compounds may be graphically represented by'the
following formula:
v‘ Q j'FT
~"atively wide range of compounds. In fact, it may
generally be saidthat‘ any acidv previously known
to be capable of promoting esteri?cation will be
satisfactory for my purpose. Speci?c examples of
~ °1i7°<i?i*‘’i*i*°i' ,
“such acids are: p-toluene-sulfonic' acid, sulfuric
acid, hydrochloric acid, and the like.
The alkyl levulinates and 2-nitro-1,3-propane
wherein the substituent R may be either hydrogen‘
diols employed in carrying'out the process of the
present invention likewise maybe selected from a
Y wide variety of compounds.-
or alkyl, and R1 represents an alkyl group. Com
pounds of the above type are prepared by reacting
a suitable 2-nitro-1,3-propanediol with an alkyl
levulinatepin the presencefof' a small" quantity of
acid catalyst. The process is preferably? eifec'ted " 20_
by heating the reaction mixture in ltheiiprés‘en‘cei
of an'inert water-'immiscibleli'quid‘such asbené
zene, toluene or a similar substanceyiniorder 'to ‘
remove- the water produced substantially ' a's“‘it‘ is?
is preferably"
heated at its re?ux temperature until?approxi
mately the theoretical quantity of water has-been
Typical examples of ,
alkyl levulinates operative in my process are
methyl levulinate, butyl levulinate, hexyl'levulin
ate, decyl levulinate, and the like.‘v Examples of
suitable ‘2~nitro-‘1,3-propanedi0ls are 2-nitro-1,3
propanediol, 2-nitro-2-methy1-1,3-propanediol;2
nitric-2"-ethyI-L3-propanédiol, ‘,2 - nitro-2-propyl
1,3-propanediol, ‘2-nitroe2-butyl-1,3-propanedioh;
and the like.
My invention may be furtherillustrated by the
, following speci?c examples:
To a mixture consisting of 149 g. of '2-ethyl-2
removed. _ Thereafter, distillation is 'dis'continued;v
and the mixture washed with water to-remove the
nitro-1,3~propanediol, 200 g. of butyl levulinate
catalyst. Separation of the inert water-immis-‘
toluene sulfonic acid. This mixture was then
heated to re?ux temperature and the Water pro
cible liquid and water, as well as other‘impurities
is readily accomplished by distillation. The inert
liquid and Water are removed at atmospheric
pressure, while the higher boiling impurities, such
and 300 .cc. of benzene, was added 1 g. of para
duced during the ketalizationremoved with ben
zene, the latter being continuously returned to
the distillation ?ask. After about twenty-four
as, unreacted alkyl levulinate or 2-nitro-1,3-pro— 35 hours, 16.5 cc. of water was removed, heating was ‘
panediol are separated from the ketal thus pro
then discontinued, and the mixture washed with
duced by distillation under reduced pressure.
cold water. The major portion of the benzene
Further purification of the desired product which
was then distilled off at atmospheric pressure
is obtained as a residue may be readily effected by
40 while the last portions thereof were removed at
distillation under relatively high vacuum.
90° C. (30 mm.). The crude butyl-2-methyl-5
One of the highly surprising features of the
ethyl-5-nitro-2-m-dioxanepropionate was then
process of the present invention is the fact that
distilled in vacuo. A fraction was collected be
said process has been found to be operative only
low 125° C. (5 mm.) and consisted chie?y of unre-'
with 2-nitro-1,3-propanediols. Attempts to carry
out the same type of reaction with the ordinary 45 acted butyl levulinate. The pure ketal boiled at
190° C. (3 mm.) and amounted to 219 g. corre
glycols such as ethylene glycol or with the trihy
sponding to a yield of 72% of theory.
dric nitro alcohols, such as, tris(hydroxymethyl) nitromethane have been completely without suc
Analysis: Calculated for C12H25NO6-gN, 4.62.
cess. With the ordinary glycols, comp1ex mix— . Found: N, 5.15.
tures of products are obtained, which cannot be 50
Example II
separated, whereas, with compounds such as tris
(hydroxymethyl) nitromethane, no reaction what
In accordance with the procedure described in
ever was observed to occur. In the case of the 2'
nitro-1,3-propanedio1s, however, the reaction in
Example I, ethyl 2-methyl-5-ethyl-5-nitro-2-m
dioxane-propionate was prepared from 2-nitro
volved appears to be quite general and is readily 55 2-ethyl-l,3-propanediol and ethyl levulinate in
prise mixing a 2-n'itro-1,3-pr0panedio1 with an’
the presence of approximately 1 g. of sulfuric:
acid. The product thus obtained was a crystal-v
line compound, melting at 83° C; and was ob
tained in a yield corresponding to 60% of theory.
alkyl levulinate in the presence of an esteri?ca
tion catalyst and an inert water-immiscible
liquid, heating the resultant mixtureto its re
?ux temperature, removing'the water in a vapor
ous state with? said water-immiscibleliquiaand. _
Analysis: Calculated for C12H21NOs——N, 5.09.
Found: N, 5.66. Molecular weight: found 269;‘
recovering the aforesaid’ substituted" 5-nitro-1,3- 7
theory, 275.
It is to be speci?cally understood that I in’ dioxane.
5. In a process ‘for the preparation of substi
no Way desire to limit
the compounds disclosed in the speci?c. examples ‘.10. -tuted. 5,-nitro-1,3-dioxanes of the formula:
given above. On the contrary, as previously. in-.
dicated, the process involved is generally appli-I '
cable to any alkyl levulinate and any 2-nitro+1,3‘- _
' i- ?
The new ketals of the present inventionhavef 15..
on, e
been found to be useful ‘as placticizers for various . >
?lm formingrmaterials, particularly‘ thosecona ,; -
sisting essentially of vinyl chloride polymers.
' in'which the substituent B. represents a member ‘
Other uses of these compounds will be readily 20 selected from the ‘group consistingof hydrogen
apparent to those skilled in the art.
havingbeen described; what. and’ alkyl; and R1 is alkyl, the steps whichcom
‘ My invention now
prise mixing} an alkylhlevulinate with a 2énitrow V
I claim is: Y
1. Substituted 5.-nitro'-l,3-dioxanes
l;3'-propanediol;in the presence of an'esteri?ca'i.
the i
following vgeneral formula;
tion catalysir heating .the resultant mixture and ~
recovering‘ a compound of? the aforesaid g-formula.
6. In "a process for‘ the preparation of‘; sub-,- _
stituted 5-nitro-1,3,=dioxanes of
the formula:
V '
wherein the- substituent B. represents, a. member ' selected fromthe group-consist‘mg: of; hydrogen
and alkyl and R1 is alkyl, ' ‘
2. Butyl 2 - methyl #- 5 - ethyl - 5 - intro-2 ~ m
’ dioxane-propionate'.
5-ethyl-5-nitro-2-msdioxane -
V >4'.;In a’ process forthe preparation'ofgsube
stitutedV-S-nitro--l,3+dioxanes having the‘ formula: -
in which the substituentLR represents a member
selected from'the group consisting of hydrogen
is alkyl, the: steps-which com
prise - mixing a Z-nitro-l?-p-propanediol with, - an ;
reilkyllevulinateinthe presence of an esteri?ca»
the resultant
_ n
tion catalyst-iandr‘benzene,
mixture to its re?ux temperature,v removingrthe
water inayaporous state with said benzene and
45 recovering'the, aforesaid substituted;5—nitrog1,3->I ‘
. '1‘.>Theprocessof claim 6 in which the alkyl
levulinate is ‘butyl levulinate and the -2-nitro-1=,3-v
propanediol is 2-nitro-2-ethyl-1,3-propanediol.
'8; The process of claim 6 in which the alkyl
in which the substituent R represents a member
selected from the class consisting of hydrogen‘
and halkyl. and B1 is alkyl, the steps which com:
50 levulinate is ethyl levulinate and the 2-nitro-l,3-é
propanediol is 2-nitro-2-ethyl-1,3-propanediol. .
Без категории
Размер файла
276 Кб
Пожаловаться на содержимое документа