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Патент USA US3021351

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United States Patent 0 "ice
3,021,341
Patented Feb. 13, 15562
2
1
EXAMPLE I
3,021,341
Preparation of S-(B-hydroxyethoxy)-1-pr0pyne by
Elkhart,
Willard J. Croxall and Norman D. Dawson, Elkhart,
Ind., assignors to Miles Laboratories, Inc.,
Ind., a corporation of Indiana
Propargyl alcohol (1-propyn-3-ol) (200 gms., 3.58
NIETHYLENE DIOXANES
alternate method
'moles) was cooled to 10° C. and 56 gms. (1.0 mole)
of KOH was added in portions. After solution of the
KOH, ethylene chlorohydrin (56 gms., 1.0 mole) was
added dropwise at a low temperature (El-14° C.). The ice
This invention relates to new and useful heterocyclic
bath was removed and the mixture warmed slowly.
10
compounds and to methods for their preparation. _More
Potassium chloride separated as the temperature in
No Drawing. Filed Feb. 23, 1960, Ser. No. 10,022
8 Claims. (Cl. 260-3406)
speci?cally, the present invention pertains to substituted
dioxanes corresponding to the following general formula:
creased. After one hour at 70—80‘’ C., the mixture was
cooled to 20° C. and ?ltered. The clear ?ltrate was dis
tilled under water pump vacuum using a ten-inch column.
15 The excess propargyl alcohol was removed at 25-30°
C./ 12-14 mm. The product was collected at 75~80°
C./ 12-14 mm. Yield, 60—70 gm. (60-70%); refractive
index, nD25 1.4508.
However, where both R2 and R3 in the formula for
wherein R1 is hydrogen, lower alkyl, lower alkenyl or a 20 3-alkyn-3-ol are alkyl substituents, i.e. with a tertiary
alkynyl alcohol it is necessary to use potassium butoxide
phenyl group; R2 to R5 are hydrogen, lower alkyl or
rather than KOH as condensing agent.
phenyl groups provided that R2 and R3 are not both
The compounds of this invention are valuable due to
hydrogens. Representative examples of this class of com
their
capability to polymerize or copolymerize with other
pounds are: 2-methylene-3,3-dimethyl-1,4-dioxane, 2
methylene-3-n-propyl-1,4-dioxane, 2-methylene-3-methy1 25 polymerizable monomers to form polymers or copolymers
3-ethyl-1,4-dioxane.
having utility as adhesive materials, protective coatings
and the like. More speci?cally, for example, when
formed by re?uxing an appropriate alkynyl ?-hydroxy
ethyl ether of the general formula
Z-methylene dioxanes polymerize readily.
The compounds of this invention can be conveniently
R;
0/
R5
catalyzed with a small amount of boron ?uoride, these
For instance, upon hydrogenation (see examples) com
lilH~CH-OH
pounds are obtained having utility as specialty solvents
for many organic compounds. It is evident that these
compounds
\o-ozom
133/
These compounds are further useful as intermediates.
30
also
undergo . halogenation,
particularly
35 bromination and chlorination, and other addition reac
R2
tions typical of unsaturated compounds.
The following examples will illustrate the various com
pounds within the purview of this invention and the
methods of their preparation. Particularly, the following
Decalin, dibutyl Carbitol, dibutyl Cellosolve, etc. In
consequence of this treatment, the alkynyl ethers are 40 example, Example II, illustrates in great detail the process
of making 2-methylene-3,3-dimethyl-1,4-dioxane as a
cyclized to yield substituted dioxanes of the formula given
representative compound. These examples are given for
hereinabove.
purposes of illustration only. It is to be understood that
The alkynyl B-hydroxyethyl ethers used in this reaction
this invention is not limited to the exact disclosure. .
can be prepared by reacting commercially available sub
wherein R1 to R5 are as indicated above, with potassium
hydroxide in an organic solvent, such as xylene, toluene,
stituted acetylenically unsaturated alcohols, l-alkyn-3-ols,
45
EXAMPLE II
with lower alkylene oxides, such as ethylene oxide,
2-methylene-3, 3-dimethyl-1 ,4-di0xane
propylene oxide or butylene oxide or the like in the
presence of born ?uoride (BF3) as a catalyst. This con
densation reaction can be represented graphically by the
PREPARATION OF 3- ( Ali-HYDROXYETH'OXY) -3-METHYL-1
BUTYNE
50
Into a three liter ?ask was charged 620.4 gms. (7.38
moles)
of
methylbutynol
(3 - methyl - l - butyn-B-ol)
Three ml. of 3% BF3 in ether was added as a catalyst and
the ethylene oxide bubbled in at a slow rate. The tem
perature of the reaction mixture was maintained at 25
55
30° C. with an ice bath. The ethylene oxide uptake was
~ 63 gms. (1,43 moles) in one hour. The reaction mixture
was adjusted to pH 7 with solid sodium methoxide and
wherein R1 to R5 have the signi?cance ascribed to them
the unreacted methyl butynol recovered by distillation
at atmospheric pressure (547 gms.). The remaining
An alternate method of synthesis of the starting mate 60 liquid was distilled rapidly and collected at 70—l20°
above.
'
rials contemplates the use of lower alkylene chlorohydrins
' in the presence of potassium hydroxide in accordance with
C./l4 mm. Hg. This, in turn, was fractionated through
a 12-inch column packed with stainless steel saddles. The
the following equation:
65
desired compound, 3 - (?-hydroxyethoxy)-3-methyl-1
butyne, was collected at 80—81° C./20 mm. Hg. The
yield was 58.3 gms. (52%) based on ethylene oxide and
the refractive index (211325), 1.4405.
PREPARATION OF 2-METHYLENE-3,3-DIMETHYL-1,4
DIOXANE
wherein R1 to R5 are as indicated hereinabove.
This
alternate method is described in greater detail by the fol
lowing example:
70
A 500 ml. ?ask equipped with stirrer, thermometer,
dropping funnel and distilling condenser was charged
with 175 ml. of Decalin and 10 gms. of solid potassium
3,021,341
3
hydroxide. This mixture was heated to 170—175° C. and
4
methyl-1,4-dioxane which on catalytic hydrogenation ab
sorbed the theoretical amount of hydrogen to give 2
the above propargyl ?-hydroxyethyl ether added drop
wise. As the cyclic compound formed, it vaporized, dis
methyl-3-n-propyl-1,4-dioxane and 2,3,3-trimethyl-1,4
tilling from the reaction mixture and was collected in a
dioxane.
receiver. The cyclized material was fractionated through
Nuclear magnetic resonance studies were conducted on
a 12-inch column. The 2-methylene-3,3-dimethyl-1,4
dioxane was collected at 136~140° C_.. The yieldwas
18.5 grns. (35%). and the refractive index (111525),‘ 1.4480.
REDUCTION OF 2-'\IETHYLENE-3,3-DIMETHYL-1,4
.
v
moxanrn
’
Z-methylene - 3,3 — dimethyl - 1,4 - ‘dioxane and 2,3,3-tri
methyl:1,4-dioxane. The ?ndings proved conclusively
that compounds having the structure of a 1,4-dioxane
were indeed formed'in consequence of the treatment de
10
scribed above. Furthermore, analytical ‘data also point
to the structure of a 1,4-dioxane.
The above 'Z-methylene dioxane (16.3 g., 0.127 mole)
What is, claimed is: V
was dissolved in 100 ml. of tetrahyd'rofuran and a small
v
_1. A substituted heterocyclic compound having "the
formula:
amount of platinum oxide catalyst added. The mixture
was shaken on the Parr apparatus at an initial hydrogen
pressure of 51v p.s.i. Hydrogen uptake began'immediate
ly and nine pounds of. the theoretical ten pounds was ab~
sorbed in thirty minutes. .The' ?nal pound required ‘an .
additional two hours, andv ?fteen minutes. The hydro
genation mixture was ?ltered to remove the catalyst 'and
the ?ltrate distilled. The solvent, tetrahydrofuran, was 20
recovered, leaving a‘yellow oil. Thisoil was distilled
and a clear liquid collected at 142-145" C.
The'yield . .
wherein R1 is selected from the group consisting of_hydro
'gen, lower alkyl, lower alke'nyl and phenyl and R2,'R3, R4
‘and
R5 are selected from they group consisting of hydro
and the refractive index (nD25), 1.4326. . .
. .
gen, lower‘ alkyl and phenyl, provided that R21-and'R3'are
In accordance with the above, process description other 25 "not
both'hydrogens.
propargyl ?-hydroxyethyl ethers were “ prepared and
of 2-,methyl-3,3_-dirnethyl-1,4-dioxane was'10‘g. (61.5%)
cyclized as follows:
7
V
2. '2-methylene-3,3-dirnethylf1,44dioxane.
"'3. 2-'methylene-i3-‘inethyl-'3iethyl;1,44dioxane.
4. Z-rnethylene-3-n-propyl-1,4-dioxane.
W
EXAMPLE ‘III, U
30
2-methylené-3-n-propyl-1,4-dioxane
l-hexyne-S-ol was reacted withethylene oxide 'to yield
3—(13-hydroxyethoxy)-l-hexyne with a"B.VP. of 94-95"
‘ 5. The method of producing‘a substituted heterocyclic
“compound having" the ' formula
.1?‘ .Rs
CH-CH\
C./ 14 mm. Hg and a refractive index (211325) of 1.4455.
The cyclization of this product‘was carried outfin
toluene, giving Z-methylene-3-n-propyl-1,4-dioxane,~ hav
35
\
R3
index (nD25) of 1.4484. Yield, 671.5% of the theoretical
amount based on'the starting material.
_,
This compound was reduced by catalytic‘ hydrogena
/0
/C-\—c\
7 ‘R1 \icHRr
ing a B.P. of 62—63° C./14 mm. Hg ‘and a refractive
40
wherein R1, is selected from the group consisting of hy
drogen,'lowerv alkyl, lower alkenyl'and phenyl, ‘and R2,
tion in methanol, yielding 2-methyl-3-n-propyl-1,4
R3, R4‘ and R5 are selected from the group consisting of
dioxane with a B.P. of 61-62° C. and a refractive‘ index
hydrogen, lower alkyl and phenyl, provided thaf'Rz‘ and
R3 are not both hydrogenIwhich comprises heating at a
(nD25) of 1.4432. Yield, 73%.
temperature of from 100‘‘- C. to 200°~ C.' a compound of
45 the formula
' EXAMPLE 1v
Z-methylene-3-methyl-3-ethyl-L4-dioxane
R; > R5
r/hn-duion
3-methyl-1-pentyn-3-ol was reacted with ethylene oxide
yielding 3-(5-hydroxyethoxy)-3-methyl-1-pentyne with a
0\
B.P. of 89-92” C./1_6 mm. Hg and a refractive index
.
50
7 011,25) of 1.4447.
dibutyl Carbitol. yielding 57.5% of 2M-methylene-3
C—CEOR1
/ \
Ra ‘Ra
This propargyl [i-hydroxyethyl ether was’ cyclized' in
wherein R1, R2,: R3, R4‘ and R5 are as indicated herein
before, with potassium hydroxide in “an” organic'solvent
methyl-3-ethyl-1,4-dioxane with a‘, B.P. ‘01557-58’ C./ 14
and taking'otf overhead the desired compound.
mm. Hg and a refractiveindex (nD25) of ‘1.4522, ,
In tetrahydrofuran this compound was quantitatively
55 9 6. The ‘method _ of
producing
2-methylene-3,3-di
' hydrogenated. to 2,3-dimethyll3-ethyl-1,4-dioxane with a
methyl-1,4-dioxanewhich.comprises heating atua tem
B.P., of 57—58° C./14"mm. Hg‘ and a'refractive‘index
perature of‘ from 170° C. to 175° C. 3-‘(B-hydroxy
(nD25)
of 14368.-
'
'
V
_,
_
v
,_
ethoxy)-3'-methyl-1-butyne with potassium hydroxide in
.
'Likewise, ,1-butyn-3-ol and _3,5-dimethy1-l-hexyn-3lol
were reacted with ethylene oxide yielding, respectively,
3-(B-hydroxyethoxy)-1-butyne with a B.P. of 74-76"
C./ 14 mm. Hg and a refractive index (ring?) of 1.4413
and 3-(,B-hydroxyethoxy)-3,5-dimethylJ1-hexyne with" a
B.P. of 91-127° C./ 14 mm. Hg and a refractive index
(nnzs) of 1.4455. These alkynyl ,B-hydroxyethyl ethers
were ,then cyclized to give 2-methylene-3-methyl-1A
,dio'xane and v2-methylene-3-methyl-3-isobutyl—1,4-diox
ane, respectively.
PROOE 0F STRUCTURE
Alkynyl ?-hydroxyethyl ethers which are monosubsti
an organic solvent and taking oif overhead'2-methylene-3,
60
3~dimethyl,-1,4-,dioxane.
,
I
7. The method of producing 2-methylene-3-n-propyl-1,
4,;dioxane which comprises heating at a temperature of
from "170“ C. to 175° C. 3-(?-hydroxyethoxy)-1-hexyne
with potassium hydroxide in an organic solvent and tak
65 ing oif overhead 2-rnethylene-3-n-propyl-1,41dioxane. ,
8. The method of producing 2-methylene-3-methyl-3
ethyl-1,4-dioxane which comprises heating at a tempera
ture of from 170“ C. to 175° C. 3-(l3-hydroxyethoxy)-3
methyl-l-pentyne with'potassium hydroxide in an organic
solvent and ‘taking 01f overhead 2-methylene-3-ethyl-L4
dioxane.
'
tuted or disubstituted in the 3-position, e.g. 3-(?-hydroxy
ethoxy)-1-hexyne and 3-(,6-hydroxyethoxy)-3-methyl-1
butyne yielded, respectively, as‘ shown1above,_2-methyl
ene - 3 - n - propyl-lA-dioxane ‘ and“ '2ime'thyléne-3,'3-'di
References Cited in the'?le of- this‘ patent
'"Summerbell et‘al.: J. ‘Am. Chem. ‘Soc; ‘vol. ‘79,'pages
75 6219-21 (1957).
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