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Патент USA US3093699

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United States atent
1
W
3,093,689’
Patented June 11, 1963,
2
is apparently responsible for the different type of product
3,093,689
HYDROXY HALOGENATED ETHER
‘
_
PRODUCTION
Kenneth B. Cofer, Pasadena, and Robert W. Fourie,
Houston, Tex., assignors to Shell Oil Company,‘ New
York, N.Y., a corporation of Delaware
N0 Drawing. Filed July 8, 1960, Ser. No. 41,475
6 Claims. (Cl. 260-613)
which is produced in high yield. These are halo-substi
tuted hydroxy ethers of predetermined composition which
are not only useful as solvents and as plasticizers for
resins but also advantageous intermediates for the produc
tion of other desirable compounds, particularly epoxy
ethers which are starting materials ‘for resins and other
products.
'
,Any of the numerous ethylenic alcohols can be used in
This invention relates to the production of halo-substi 10 the new process. One especially preferred subgroup of
tuted hydroxy ethers and especially to the manufacture of
starting alcohols are the water soluble beta,gamma-mono
these compounds from unsaturated alcohols.
ethylenic monohydric alcohols having three to ?ve carbon
There are several routes whereby halo-substituted hy
atoms per molecule. Typical examples of alkenols of this
droxy ethers can be made'using conventional chemical
kind are, allyl alcohol, methallyl alcohol, crotyl alcohol,
operations. For instance, an ether can be halogenated to 15 methyl vinyl carbinol, dimethyl vinyl carbinol, 3-methyl-2
introduce a plurality of halogen atoms per molecule and
buten-l-ol, methyl isopropenyl carbinol, and the like.
a part of these halogen atoms can be hydrolyzed to hy
Examples of other suitable starting ethylenic alcohols are,
droxy groups by reacting with sodium hydroxide or the
for instance, S-buten-l-ol; 3-pen-ten-l-ol; 3-methyl-3
like. Alternatively a polyhydroxy ether can be reacted
butene-l-ol; Z-methyl-B-butene-l-ol; methyl allyl carbinol;
producing mixed products since there is no way of con
4-methyl-4-penten-l-ol; 2,3-dimethyl crotyl alcohol; ethyl
allyl carbinol; 1-heptene-4-ol; methyl ethyl allyl carbinol;
dimethyl allyl carbinol; 2,4-dimethyl-lshepten-4-ol; 1
decen-4-ol; 3,7-dimethy1-2-octen-1-01; IO-undecen-l-ol; 11
trolling which of the halogens and hydroxyl groups will be
dodecen-l-ol; oleyl alcohol, etc. Instead of the foregoing
with dry hydrogen halide or with phosphorous pentahalide
to partly replace the hydroxyl groups by halogen. Besides
low yields, these methods have the disadvantage of usually
converted in the different operations. On this account it 25 open chain aliphatic hydrocarbon alcohols, cyclo aliphatic
hydrocarbon alcohols such as 2-cyclohexenol; 3-cyclo
is customary to rely upon reaction of an epihalohydrin
hexenol; 2 - ethylidene - 1 - cyclohexanol; 3-cyclohexenyl
with an alcohol for production of halogenated hydroxy
ethers. The limited availability of low cost epihalohydrins
methanol, and the like can be used. Another subgroup
of suitable starting ethylenic alcohols are the aryl-substi
seriously restricts the usefulness of this method and makes
tuted ethylenic alcohols and the alkenyl-substituted aro
it prohibitively expensive in most cases where the starting
matic alcohols of which the following are representative
epihalohydrin must be especially synthesized for the reac
tion.
\
An important object of the invention is the provision of
examples, alpha-vinyl-benzyl alcohol; l_-phenyl-3-buten-2
o1; 2-phenyl-4-penten~2-ol; para-vinyldbenzyl alcohol and
3-phenyl-3-pcnten-2-o1.
a new and economically attractive method for the produc
tion of hydroxy halogenated ethers from unsaturated alco 35 Starting alcohols which contain more than one hydroxyl
group and/ or more than one ethylenic double bond in the
hols. Another object is the direct production in a single
step, of halogenated hydroxy ethers from ethylenic alco
molecule can be used in the new process although halo
substituted hydroxy ether mixtures of greater complexity
hols. Still another object is to provide a new process
whereby halo-substituted hydroxy ethers of predetermined
will be obtained. Polyhydric ethylenic alcohols which
?xed composition can be efficiently produced. A special 40 can be employed ‘are, for instance, 2~butene-l,4-diol;nl
object is the production of halogen-substituted hydroxy
butene - 3,4 - diol; Z-ethyl-l~phenyl-3-butene-1,2-diol; 5
ethers which can be either symmetrical or unsymmetrical
vinyl-1,3-dimethanol benzene; 1,4-dihydroxycyclohexene
ethers depending upon the choice of the starting alcohol
(reactants. Further objects and advantages of the invention
will be apparent from the following description of the new
2; 1,2-dihydroxycyclohexene-3 and the like. Examples of
process.
polyethylenic ‘alcohols which can be similarly used are,
vinyl allyl carbinol; allyl propenyl carbinol; diallyl methyl
carbinol; geraniol; linalool, 2,4-cyclohex-adienylmethanol;
In accordance with the invention halo-substituted hy
droxy ethers are produced by reacting an ethylenic alcohol
with a hypohal-ogenous acid. Ethers having halogen and
divinylbenzyl alcohol; and 3,4-dihydroxy-1,5-hex-adiene.
hydroxy substituents on both groups attached to the ether
oxygen atom are produced when the alcohol reactant is
of the foregoing alcohols which are seen to be alcohols
of up to 18 carbon atoms per molecule containing only
carbon, hydrogen and hydroxyl oxygen atoms. Halo
gen, ether, ketone, ester and like substituents which are
unreactive under the conditions of the new reaction are
ehylenic alcohol exclusively. By adding a non-ethylenic
‘ alcohol to the reaction mixture an unsymmetrical halo
substituted hydroxy ether in which one of the groups
Substituted ethylenic alcohols can be employed as
starting materials in the process of the invention instead’
attached to the ether oxygen is the same as that linked to 55 the preferred type of substituents.
the hydroxyl group of the non-ethylenic alcohol is pro
Examples of such
substituted ethylenic alcohols are, for instance, l-chloro
duced by the new process. In both cases products may
be obtained which are mixtures of isomeric ethers in which
halogen is linked to one of the carbon atoms of the
methoXy-Z-propen-l-o-l; 1-allyloxy-2-hydroxybutene-3; 3-.
hydroxy-4-cyclohexene-l-one; 1-acetoxybutene-2-ol-4 and
ethylenic group of a starting ethylenic alcohol and an ether 60
oxygen is linked directly to the other carbon atom of that
group in one ether and the halogen and ether oxygen link
ages are reversed in their attachments to the carbon atoms
of that‘ethylenic group in an isomeric ether product.
Production of halo-substituted hydroxy ethers in this
way is readily "carried out on a commercial scale in an
e?icient and economical manner. It was unexpected to
3-buten-2-ol; 5 - chloro - 3 - methyl-2,4-hexadien-l-ol;
the like.
1
a
When using ethylenic alcohols which have a solubility
in Water ofless than about 25 percent by weight, at ordi
nary temperature, it is advantageous to add to the reac
tion mixture a mutual solvent for the ethylenic alcohol
and the hypohalogenous acid solution with which it is to
be reacted. Su?icient of the mutual solvent should be
used to make the concentration of the ethylenic alcohol in
hypohalogenous acid solution at least equal to 50 per
?nd that this single step‘ process will give these useful
cent by weight.
products. Instead halohydrination products of the start 70 The hypohalogenous acid with which the ethylenic
ing ethylenic alcoholrnight have been predictedas the
alcohol is reacted is preferably an aqueous solution of
predominant product. A diiferent mechanism of reaction
hypochlorous or hypobromous acid although hypo?uo;
3,093,689
rous or hypoiodous acids can also be used. The hypo~
halous acid can be made in the usual way by reacting
the corresponding halogen with water. Instead of a pre
formed solution of the acid, the hypohalogenous acid can.
be formed in the reaction mixture during the process of
the invention by feeding halogen and water to the re
actor. Preferably a large molar excess of water to halo
gen, for example, about 5 to about 50 or more moles per
mole of halogen, is used. Alcohol hypohalites, such, for
example as ethyl hypochlorite, tertiary butyl hypochlo
In the same way when methallyl alcohol is reacted, an
equally good yield of bis-(2-chloro-3-hydroxy-2-methyl
propyl) ether and isomers is obtained and from crotyl
alcohol and hypobromous acid bis(2-bromo-3-hydroxy
butyl) ether and isomers are obtained.
By using methyl vinyl carbinol in place of the allyl
alcohol of Example I, a good yield of bis(3-chloro-4
hydroxy-Z-butyl) ether and isomers is realized. With
either 2-rnethyl-2~buten-l-ol or methyl isopropenyl car
10 binol and hypobromous acid as the reactants the product
rite, n-butyl hypobromite, and the like are another source
of hypohalogenous acid for the reaction of the invention.
The hypohalogenous acid, whether preformed or made
in situ is desirably used in an overall ratio of about one
mole per mole of ethylenic alcohol to be reacted.
is 3 - (Z-bromo - 3 - hydroxy-Z-methylbutoxy)~2-bromo-2
Higher proportions of alcohol can be employed although
usually at a sacri?ce of plant capacity. Higher propor
tions of hypohalogenous acid, or of halogen when in situ
the same way, reaction of alpha-vinyl-benzyl alcohol
hypohalogenous acid production is being used, to alcohol
chloro-3,4-dihydroxy - 1 - butoxy) - 3 - chloro-1,4-butane
methylbutanol-l and isomers in good yield.
When using 2-cyclohexenol as the ethylenic alcohol in
the method of Example I the ether product is bis(2
chloro-3-hydroxycyclohexyl) ether and its isomers. In
gives bis(2-chloro~3-hydroxy-l-phenylpropyl) ether and
isomers. With 2-butene-1,4-diol the product is 2(2
are feasible in the process but are less preferred because 20 diol and isomeric hydroxy-chloro ethers.
of the greater danger of by-product formation. An ex
With a substantial molar excess of divinyl carbinol to
ception to this rule is in reactions with polyethylenic al
hypochlorous acid at all times in the reaction one can
cohols where higher ratios of hypohalogenous acid will
obtain bis(1-vinyl-2-chloro-3~hydroxypropyl) ether and
be desirable when one wishes to obtain a halohydrinated
isomers in signi?cant yield or by the use of larger amounts
product instead of a halo-hydroxyether containing one or 25 of hypochlorous acid, the chlorohydrination products of
more ethylenic groups. As a general rule mole ratios
this unsaturated chlorohydroxy ether, particularly bis(2,4—
used will be in the range of about 0.5 :l to about 2:1,
idichloro-l,5-dihydroxy-3-amyl) ether and isomers can
more preferably about 0.9:1 to about 1.1:1 when react
be obtained in substantial yield.
ing monoethylenic alcohols.
The new reaction is carried out advantageously in the
liquid phase, preferably at ordinary temperatures, but
As previously pointed out, the reaction can be carried
out having in the reaction mixture another alcohol or
a phenol which takes part in the reaction as well as the
higher or lower temperature can also be used. Tem
ethylenic alcohol. In this modi?cation of the invention
peratures in the range of about 0° to about 100° C. are
the product will be an unsymmetrical ether in which one
suitable. Atmospheric or elevated pressures can be used
of the groups attached to the ether oxygen atom cor
and either batch, continuous or intermittent method of 35 responds to the other alcohol or phenol minus a hydroxyl
reaction can be employed successfully.
The following examples illustrate in more detail, suit
able methods for applying the process of the invention.
Example I
group while there is also linked to the ether oxygen atom
a halo hydroxy radical derived from the ethylenic alco
?ux condenser, and chlorine-dispensing tube. The ?ask
equal mole ratios of the two different types of hydroxy
compounds is advantageous. However, ratios of the
hol. This method of reaction can be carried out under
the same conditions as used in reacting a single ethylenic
40 alcohol or mixtures thereof with hypohalous acid as
This example illustrates the production of di-(chloro
previously described. Lower alkanols are an example
hydroxypropyl) ethers by reacting allyl alcohol, chlorine
of one subgroup of saturated alcohols useful in this
and water.
modi?cation of the invention.
One hundred and seventy grams of allyl alcohol, along
The ratio of ethylenic alcohol to other alcohol or
with ?fty grams of water, were charged to a one-liter
phenol which can be used in this modi?cation of the
reaction ?ask equipped with a stirrer, thermometer, re
invention can be varied widely. Usually approximately
was immersed in a water bath for temperature control.
Approximately 142 grams of chlorine were bubbled into
the reaction ?ask over a two~hour reaction period.
During the reaction the contents were rapidly stirred
while the temperature was controlled between 0° C. and
25° C. by the addition of ice to the water batch.
After reaction the hydrochloric acid produced from
the reaction of chlorine with water to form HOCl and
order of about 0.121 to about 1.5:1 more preferably
about 0.9:1 to about 1.1:] moles of ethylenic alcohol to
other hydroxyl compound, i.e. alcohol or phenol, are
suitable.
The following examples illustrate this modi?cation of
the invention in more detail.
Example II
HCl was neutralized with about 70 grams of NaOH dis
solved in 200 cc. of water. During the neutralization
This example illustrates the production of 2-chloro-3
the contents of the ?ask were kept at about 0“ C. to pre
hydroxypropyl n-butyl ether and 2-butoxy-3-chloropro
vent reaction of the chlorohydrin ethers with the NaOH.
panol from n-butanol, allyl alcohol and hypochlorous
After neutralization, the water and excess allyl alcohol 60 acid.
were distilled off under Vacuum (200 mm. Hg). The
Two hundred grams of normal butyl alcohol, along
product was then stabilized by heating to about 110° C.
with 50 grams of water and 58 grams of allyl alcohol,
at 200 mm. Hg pressure for a period of 30 minutes.
were charged to a one-liter reaction ?ask equipped with a
After stabilization the crude ether product was ?ltered to
stirrer, thermometer, re?ux condenser, and chlorine-dis
remove solid salt. The product was further puri?ed by 65 pensing tube. The ?ask was immersed in a water bath
distilling off the dichlorohydrin and monochlorohydrin
for temperature control. Approximately 71 grams of
contaminants by stabilizing to a temperature of 110° C.
chlorine was bubbled into the reaction ?ask over a two—
at 10 mm. pressure. About 180 grams of product was
hour reaction period, during which time the contents were
obtained, which was identi?ed as chlorohydrin ethers.
rapidly stirred and the temperature was controlled be
The chief components of the product appear to be bis(2 70 tween O" C'. and 25° C. by the addition of ice to the water
chloro-3-hydroxypropyl) ether and its isomers 2-chloro
bath.
3-hydroxypropyl 3-chloro-2-h},’droxypropy1 ether, 2-chlo
After reaction the hydrochloric acid produced during
ro-3-hydroxypropy1 1-hydroxymethyl-2-chloroethyl ether
the reaction was neutralized with about 40 grams of
and 3-chloro-2-hydroxypropyl l-hydroxymethyl-Z-chlo
NaOH ‘dissolved in about 150 cc. of water. During the
75 neutralization step, the contents of the reaction ?ask were
roethyl ether.
3,093,689
5
6
kept at about 0° C. to prevent reaction of the chloro
hydrin ethers with the NaOH. After neutralizationthe
We claim as our invention:
1. A process for producing an unsymmetrical halo
water and excess normal butyl alcohol were distilled oli
substituted hydroxy ether which comprises reacting at
under vacuum. The product was then stabilized by heat
ing to 110° C. at 200 mm. Hg pressure for about 30
minutes. After stabilization the product was ?ltered to
about 0° to about 100° C. an ethylenic alcohol having
up to 18 carbon atoms per molecule and a member of
the group consisting of phenol and a lower alkanol with
an aqueous hypohalogenous acid solution using a mole
ratio of said acid to ethylenic alcohol of about 0.5:1
remove the solid salt. Approximately 150 grams of light
amber product was obtained, which was identi?ed as
chlorohydrin ether of normal butyl alcohol.
to about 2:1 and a mole ratio of ethylenic alcohol to
By substituting methallyl and ethyl alcohols for the 10 said group member of about 01:11 to about 1.511,.the
allyl and butyl alcohols in the above process, a good yield
concentration of the ethylene alcohol in the hypohalog
of 3-ethoxy-2-chloro-2-methyl-1 propanol and its isomer
enous acid solution as calculated Without said group
2-ethoxy-2-met-hyl-3-chloro-l-propanol is obtained. Using
member being initially at least 50% by weight, and said
isopropyl alcohol with crotyl alcohol and hypobromous
alcohols containing only carbon, hydrogen and hydroxyl
acid under the same conditions, the products are 3-iso
propoxy-Z-bromo-labutanol and its isomer 2-isopropoxy
3-bromo-1abutanol.
Similar reaction of dimethyl vinyl carbinol with tert.
butyl alcohol and H001 formed in situ gives 4-chloro
' oxygen atoms whereby an unsymmetrical ether having
attached to the ether oxygen atom (a) the radical cor
responding to said group member minus OH, and (b) a
halo hydroxy radical derived from the ethylenic alcohol
is produced.
3-tert. butoxy-Z-methylbutanol-Z and 3-chloro-4-tert.
butoxy-Z-methylbutanol-Z. With 3-butene-l-ol and n-pro
panol reacted with bromine and water, one obtains 3
2. A process for producing an unsymmetrical halo
substituted hydroxy ether which comprises reacting at
about 0° to about 100° C. an ethylenic alcohol having
up to 18 carbon atoms per molecule and a lower alkanol
with an aqueous hypohalogenous acid solution using a
bromo-4-propoxy-l-butanol and 4-bromo-3-propoxy-1
butanol.
l-cyclohexenylmethanol and methanol reacted with hy 25 mole ratio of said acid to ethylenic alcohol of about
pochlorous acid as in Example 11 results in the produc
0.5:1 to about 2:1 and a mole ratio of ethylenic alcohol
tion of l-chloro-l-hydroxymethyl-Z-methoxy cyclohexane
to saturated alcohol of about 0.1:1 to about 1.5:1, the
and 2-chloro~1-hydroxymethy1 - 1 - methoxycyclohexane.
concentration of the ethylenic alcohol in the hypohalo
Analogous reaction of 1-phenyl-34buten-2~ol and ‘ethanol
yields 1-pheny1-3-chloro-4-ethoxybutanol-2 and l-phenyl
4-chloro-3-ethoxybutanol-2. ‘From 3-hexene-2,5-diol and
isopropanol the chief product is 3-isopropoxy-4-bromo
hexane~2,5-diol when using hypobromous acid under the
same conditions.
30
genous acid solution as calculated without the saturated
alcohol being initially at least 50% by weight, and said
alcohols containing only carbon, hydrogen and hydroxyl
oxygen atoms whereby an unsymmetrical ether having
attached to the ether oxygen atom (a) the radical cor
By substituting phenol for the n-butanol of Example 35 responding to said saturated alcohol minus OH, and (b) a
halo hydroxy radical derived from the ethylenic alcohol
H there can be produced 3-phenoxy-2~chloro-l-propanol
is produced.
and its isomer 2~phenoxy-3—chloro-1-propanol.
Use of a polyol for reaction with the ethylenic alcohol
and hypohalous acid makes it possible to produce either
3. A process in accordance with claim 2 wherein the
unsymmetrical halo-substituted ether is recovered by neu
mono- or polyethers as predominant product depending 40. tralizing the reaction mixture at a temperature below that
at which the ether reacts under the existing conditions and
upon the proportions of the reactants which are employed.
then distilling.
'I‘hus reaction of allyl alcohol with ethylene glycol and
hypochlorous acid according to the method of Example
4. A process in accordance with claim 2 wherein an
II gives 2-chloro-3abeta-hydroxyethyl-l-propanol with its
alkyl 2-chloro-3-hydroxyalkyl ether is produced by re
isomer 3-chloro-Z-betaahydroxyethyl-1-propanol and 1,2 45 acting a lower alkanol with a beta,gamma~ethylenic al
kenol having 3 to 5 carbon atoms per molecule and hypo
chlorous acid.
and hypobromous acid in aqueous acetone solution, the
5. A process in accordance with claim 4 wherein the
chief products are Z-(parahydroxypheny-l) -2 [4-(ch1oro-3
alkenol is allyl alcohol and the hypochlorous acid is
50
hydroxypropoxy) phenyl] propane and its isomer Z-(para
formed in the reaction mixture by reacting chlorine with
hydroxyphenyl)-2[4-»( 1-hydroxymethy-1-2 - chloroethoxy)
water.
phenyl] propane or 2,2~bis[4-(2-chloro-3-hydroxypro
6. A process for producing a phenyl 2-chloro-3-hy
poxy)phenyl] propane and isomers depending on the
droxyalkyl ether which comprises reacting at about 0°
proportions of the reactants employed.
Still other variations can be made in the process of the 55 to about 100° C., phenol and a beta,gamma-ethylenic
alkenol of 3 to 5 carbon atoms per molecule with aqueous
invention which is not limited to the reactions which
hypochlorous acid solution using a mole ratio of said
have been given by way of illustration only nor by the
acid to ethylenic alcohol of about 0.5 :1 to about 2:1
examples which have been used to show suitable pro
and a mole ratio of ethylenic alcohol to phenol of about
cedures for conducting these new reactions. Nor is the
invention limited by any theory proposed in explanation 60 0.1:1 to about 1.5 :1, the concentration of the ethylenic
alcohol in the hypohalogenous acid solution, as calculated
of the new and improved results which are produced
without the phenol, being initially at least 5 0% by weight
by the new method.
whereby an ether having attached to the ether oxygen atom
The halo-hyd-roxy ethers whose e?icient production
bis(2-chloro - 3 - hydroxypropyl(ethane
and
isomers.
Using 2,2-bis(parahydroxyphenyl)propane, allyl alcohol
from ethylenic alcohols is made commercially feasible
(a) the phenyl radical, and (b) a chloro hydroxy alkyl
by the new process have a number of important uses.
radical derived from the alkenol is produced.
The liquid halo-hydroxy ethers are solvents ‘for resins
and the like and are useful in surface coating composi
References Cited in the tile of this patent
tions. These and higher molecular halohydroxy ethers are
convertible by reaction with sodium hydroxide or other 70 Read et al.: Jour. Chem. Soc. (London), vol. 121
base to epoxyethers which, especially in the case of the
(1922), pages 989-999‘.
polyepoxy products, are starting materials for resinous
Taylor et al.: Canadian Jour. of Research, vol. 4
products of various kinds. It will accordingly be seen
(1931), pages 119-133.
that the new process of the invention offers many ad
Williams et al.: Chem. and Met. Eng; vol. 47 (1940),
vantages and can be applied in many ways.
75 pages 834—838.
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