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Патент USA US3023216

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United States
atent
3,023,207
CC
Patented Feb. 27, 1962
1
2
In carrying out the second step of the method, the
3,023,207
POLYALKYLENEGLYCOL 3,4-DIHYDRO-2H-L3
.
phenolic compound or a solution thereof in inert solvent
‘ is added portionwise to the reaction mixture prepared.
as described above. In such operations, one molecular
BENZOXAZlN-li-YLALKYL MGNOETHERS
Raymond H. Rigterink, Midland, Mich, assignor to The
4 Dow Chemical Company, Midland, Micln, a corpora
tion of Delaware
proportion of phenolic compound is employed with each
' No'Drawing. Filed Oct. 22, 1959, Ser. No. 847,886
preparation of the intermediate condensation product.
The reaction takes place smoothly within the temperature
‘
molecular proportion of the monoether reactant used in.
5 Claims. (Cl. 260-244)
range of from 30° C. to 100° C. with the production of
' This invention is directed to polyalkyleneglycol 3,4-di
hydro-2H-l,3-benzoxazin-3-ylalkyl
sponding to the formula
monoethers
the desired product and water of reaction. Upon, comple
tion of the reaction, the reaction mixture may be frac
tionally distilled under reduced pressure to remove the
low boiling constituents including solvent and water of
corre
0
/ \OH2
R
reaction, and obtain-the desired product as a viscous
15
\\ /N-<Y-o—)..—n
liquid residue.
In an alternative method of preparing‘the new com
pounds, a 3-loweralkanol-3,4-dihydro-2H-1,3-benzoxazinel .
C
H:
corresponding to the following formula:
wherein R represents an ortho-arylene radical of the ben
zene series, each Y represents an ethylene or propylene
radical and n is an integer from 6 to 40, inclusive. The
expression “ortho-arylene radical of the benzene series”
is employed in the present speci?cation and claims to
0
refer to the divalent arylene radicals of the benzene series
H2
whose valencies are on adjacent carbon atoms in the 25
benzene ring and includes ortho phenylene radicals sub
is reacted with ethylene oxide or propylenev oxide, or a
mixture thereof, or successively with each of ethylene
oxide and propylene oxide to introduce a polyoxyalkylene
stituted by one or more substituents such as phenyl, alkyl
containingl to 16 carbon atoms, chlorine, bromine,
benzyl, and cyclohexyl.
The new compounds of this invention are viscous 30
liquids somewhat soluble in water and in many organic
solvents such as ethanol, acetone, and carbon tetrachlo
chain containing at least 5 oxyalkylene units-for thelhy-_
droxyl hydrogen in the 3-lowera1kanol-3,4-dihydro-2I-l1j
1,3-benzoxazine reactant. The number of oxyalltylene
units introduced into the molecule is somewhat dependent
upon the condition under which the reactants are. brought
ride. The compounds are useful as parasiticides, and
adapted to be employed as active constituents of com
positions for the control of Mexican Bean Bettle and 35
Southern Army Worms. The compounds are also useful
as herbicides. The new compounds may be prepared
by causing a polyalkyleneglycol aminoalkylmonoe-ther
having the formula
together, and primarily dependent upon the molar ratio
of employed benzoxazine reactant and alkylene ‘oxide.
Thus one molecular proportion of the benzoxazi'ne re-j
actant is reacted With ethylene oxide or propylene‘oxide
or a mixture thereof, in the amount of from about 5 to 39
molecular proportions of total alkylene oxide. depending
upon whether it is desired to introduce ‘from 5 to 39 alkyl
ene oxide units into the molecule. The reaction is carried
out in the presence of a catalyst which'may be an alkali
to react with formaldehyde or a formaldehyde yielding
metal hydroxide, such as sodium hydroxide, andtakesf
substance, to form an intermediate formaldehyde-poly
place readily at a temperature of from 100° to 210° C.
alkylene glycol aminoalkyl monoether condensation prod
uct. The intermediate is thereafter reacted with a phen 45 and under a pressure of from 10 to 500 pounds per
square inch. Upon completion of the reaction, the reac-;
olic compound corresponding to the formula
'
_ tion mixture may be fractionally distilled under reduced
suchpas phenol, 4-chlorophenol, 4-bromophenol, 4-meth
ylphenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol, 2,4,5
tribromophenol, 4-chloro-2-methylphenol, o-isobutylphe
nol 4-bromo-2-methylphenol, 4-tertiarybutylphenol, 2,4
ditertiarybutylphenol, Z-methylphenol, 4-hexylphenol, 4
cyclohexylphenol, 4-benzylphenol, 4-butyl-2-methylphe
nol, 4-decylphenol, 2,4,5-trimethylphenol, 4-nonylphenol,
or 4-phenylphenol to produce the desired product and
water of reaction.
'
pressure to remove any low boiling constituents and ob
tain the desired product as a viscous liquid residue.
50
The following examples illustrate the invention but
are not to be considered as limiting.
'
EXAMPLE 1
Pentaethyléneglycol-6~Chloro-3,4-Dihyiz'ro-2H
55
1,3-Benz0xazin-3-ylethyl Monoether
O
CH:
In carrying out the ?rst step of this method, the poly
alkylene glycol arninoalkyl monoether is intimately con
tacted with formaldehyde or a formaldehyde yielding 60
substance in an inert reaction medium such as methanol,
ehtanol, or dioxane. The contacting of the reactants is
Pentaethyleneglycol Z-aminoethyl monoether having an‘
carried out with stirring and at a temperature of from
index of refraction n/D of 1.4798 at 25% C. (65.3.
0° to 80° C. Good results are obtained by reacting one
grams; 0.23 mole) was gaddedportionwisc with stirring
molecular proportion of the monoether reactant With two
over a period of 15 minutes to a solution of 15 grams
Ha
molecular proportions of formaldehyde. The formalde
hyde may be employed in any readily available form
such 'as formalin or paraformaldehyde.
The amount
,
I
..
(0.5 mole) of paraformaldehyde and 0.25 gram potas
sium hydroxide in ‘100 milliliters of methanol. There
action vessel was continuously cooled during the addi
of formaldehyde employed is calculated upon the basis
tion to maintain the temperature in the range of 25°
of the monomer unit. The reaction conveniently may 70 30° C. Upon completion of the addition, 37.5 grams
be carried out in the presence of a small amount of
(0.25 mole) 4-c-hlorophenol was added in a single pore
alkali metal hydroxide as catalyst.
- tion to the reaction mixture and the resulting mixture
3,023,207
3
and had an index of refraction’ n/ D of 1.5111 at 25° C.
and an average oxyethylene content of about 10 oxyethyl
perature of approximately 75° C. The reaction mixture
was thereafter fractionally distilled under reduced pres
sure at gradually increasing temperatures up to a pot
temperature of 100° C. at 10 millimeters pressure to re
move low-boiling constituents and obtain a pentaethylene
ene units per molecule.
EXAMPLE 5
6 - chloro-3,4-dihydro-8-methyl-2H-1,3-benzoxazine-3
glycol 6-chloro-3,4-dihydro-2H-1,3-benzoxazin-3 - ylethyl
monoether product as a liquid residue. This product had
a refractive index n/D of 1.5196 at 25° C.
EXAMPLE 2
4
liquid residue. The product was slightly soluble in water
heated with stirring under re?ux for two hours at a tem
ethanol having a refractive index n/ D of 1.5693 at 25° C.
(45.5 grams; 0.2 mole), 79.2 grams (1.8 moles) of ethyl
10 ene oxide and 0.5 gram of sodium hydroxide were placed
Pentaéthyleneglycol-5,6,8-Trichloro-3,4-Dihydro~
2H-1,3-Benz0xazin-3-ylethyl Monoether
in a reaction vessel which was thereafter closed and sealed.
The reaction vessel and contents were agitated and
heated under autogenous pressure to a temperature of
120° C. and a pressure of 350 pounds per square inch
15 and thereafter maintained at a temperature of 120° C.
170° C. for twenty minutes. As a result of these opera
tions, there was obtained a polyethylene glycol-6-chloro
3,4-dihydro-8-methyl-2H-1,3-benzoxazin~3-ylethyl mono
O
ether product as a viscous liquid having a refractive index
.- Pentaethyleneglycol Z-aminoethyl monoether (108.6 20 n/D of 1.5069 at 25° C., and an average oxyethylene
.
Cl
H2
grams; 0.385 mole) was added portionwise with stirring
over a period of ?ve minutes to a solution of 30 grams
content of about 10 oxyethylene units per molecule.
EXAMPLE 6
(1.0 mole) paraforrnaldehyde and 0.5 gram of potassium
6 - chloro — 3,4-dihydro-2H-1,3-benzoxazine-3-ethanol
hydroxide in 250 milliliters of methanol. The reaction
(21.4
grams; 0.1 mole), 40.6 grams (0.7 mole) of propyl
vessel was continuously cooled during the addition to 25
ene oxide, and 0.5 gram of potassium hydroxide were
maintain the temperature in the range of from 25° to
placed in a reaction vessel which was thereafter closed
30° C. Thereupon, 98.7 grams (0.5 mole) 2,4,5-trichloro
and
sealed. The reaction vessel and contents were agi
phenol was added with stirring and the solution heated
tated and heated under autogenous pressure to a tempera
at the boiling temperature with stirring and under re?ux
for two hours. The reaction mixture was thereafter con
centrated by fractional distillation under reduced pres
sure at gradually ‘increasing temperatures of up to a
pot temperature of 110° C. at 5 millimeters pressure,
to remove low boiling constituents and obtain a penta
ethyleneglycol
5,6,8-trichloro-3,4-dihydro-2H-1,3-hen
z'oxazin-3-yle'th'yl monoether product as a liquid residue.
This product had a refractive index n/D of 1.5466 at
25 ° C. and was soluble in carbon tetrachloride and only
slightly soluble in water.
EXAMPLE 3
v Polyerhylenegiycol 6-Chl0ro-3,4-Dihydr0-2H-L3-Ben
z0xazin-3-ylethyl Monoether
6 - chloro - 3,4-dihydro-2H-1,3-benzoxazine-3-ethanol,
ture of 125° C. and a pressure of 140' pounds per square
inch and thereafter maintained at a temperature of 125 °—
140° C. for 1.5 hours. Thereafter heating was discon
tinned and the vessel and contents chilled. The reaction
vessel was then opened and to its contents were added
35 30.8 grams (0.7 mole) of ethylene oxide, and the vessel
thereafter closed, sealed and heated with agitation and
under autogenous pressure at the temperature range of
from 125 °—156° C. for a half hour. As a result of these
operations, there was obtained a polyalkyleneglyool 6
40 chloro - 3,4-dihydro-2H-1,3-benzoxazin-3-ylethyl mono
ether product as a very viscous liquid having an average
oxyalkylene content of 7 oxypropylene units and 8 oxy
ethylene units per molecule. The product had a refrac
tive index n/D of 1.4905 at 25° C. and was soluble in
carbontetrachloride.
having a refractive index n/D of 1.5830 at 25° C. (42.7
grams; 0.2 mole), 88.0 grams (2 moles) of ethylene oxide
EXAMPLE 7
6 - chloro - 3,4-dihydro-2H-1,3-benzoxazine-3-ethanol
and 0.5 gram of potassium hydroxide were placed in a
'(42.8 grams; 0.2 mole), 116.2 grams ‘(2.0 mole) of pro
reaction vessel which was thereafter closed and sealed.
pylene oxide, and 0.5 gram of caustic ‘soda were placed
The reaction vessel and contents were agitated and heated 50 in a reaction vessel which was thereafter closed and sealed.
under autogenous pressure to a temperature of 130° C. at
The contents of the reaction vessel were agitated
a pressure of 150 pounds per square inch, and thereafter
and heated under autogenous pressure to a temperature
maintained at a temperature of 130°—165° C. for one
of 150° C. for an hour and a pressure of 245 pounds per
hour. As a result of these operations, there was obtained
square
inch and thereafter maintained at a temperature
a polyethyleneglycol 6-chloro-3,4-dihydro-2H-1,3-benzox
of 150° C. As a result of these operations, there was
azin-B-ylethyl monoether product as a viscous liquid
obtained ‘a polypropyleneglycol 6-chloro-3,4-dihydro-2H—
residue. This product had an index of refraction n/D
1,3-benzoxazin-3-ylethyl monoether product having an
of 1.5063 at 25 ° C. and an average oxyethylene content
of about 11 oxyethyl'ene units per molecule.
EXAMPLE 4
Polyethyleneglycol 6,8-Dich-I0r0-3,4-Dihydr0-2H-] -3
Benz0xazin-3-ylethyl Monoéther
6,8 - dichloro-3,4-dihydro-2H-1,3-benzoxazine-3-ethan0l
having a refractive index n/D of 1.5905 at 25 ° C. (49.6
index of refraction n/D of 1.4713 at 25° C., and an
average oxy'propylene content of about 10 oxypropylene
60 units per molecule.
The product was a viscous liquid
of moderate solubility in water.
EXAMPLE 8
6 - chloro - 3,4-dihydro-2H-1,3-benzoxazine-3-ethanol
(21.4 grams; 0.1 mole), 83.6 grams (1.9 moles) of ethyl
ene oxide, and 0.5 gram of sodium hydroxide were placed
in a reaction vessel which was thereafter closed and
sealed. The reaction vessel and contents were agitated
a reaction vessel which was thereafter closed and sealed.
‘and heated under autogenous pressure to a temperature
The reaction vessel and contents were agitated and heated
under autogeneous pressure to a temperature of 126° C. 70 of 140° C. and a pressure of 400 pounds per square inch
and thereafter maintained at a temperature of 140°~160°
and a pressure of 300 pounds per square inch and there
‘C. for 1.5 hours. As a result of these operations, there
after maintained at va temperature of 126°—138° C. for
was obtained a polyethyleneglycol 6-chloro-3,4-dihydro
‘an hour. As a result of these operations, there was ob
grams; 0.2 mole), 79.2 grams (1.8 moles) of ethylene
oxide,- and 0.5 gram of sodium hydroxide were placed in
tained ='a polyethyleneglycol 6,8-dichloro-3,4-dihydro-2H
2H-1,3-benzoxazii1-3-ylethyl monoether product having
1,3-benzoxazin-3-y-lethyl monoether product as a viscous, 75 an average oxyethylene content of about 20 oxyethylene
3,023,207
5
units per molecule.
The product was a water soluble,
6 ~ chloro - 3,4 - dihydro-ZH-1,3-benzoxazine-3-ethanol
3-ylethyl monoether product as a viscous liquid having an
index of refraction MD of 1.4989 and an average oxy
ethylene content of about 10 oxyethylene units per mole
cule.
EXAMPLE 15
Cl
(10.7 grams; 0.05 mole), 85.8 grams (1.95 moles) of
ethylene oxide, and 0.5 gram of sodium hydroxide were
mole) of 3,4-dihydro~6-phenyl-1,3-benzoxazine~3-ethanol
viscous liquid having a refractive index n/D of 1.4858
at 25° C.
,
EXAMPLE 9
'
Ethylene oxide (79.2 grams; 1.8 moles), 51 grams (0.2‘
placed a pressure reaction vessel which was thereafter
were reacted together substantially as described in Ex
closed and sealed. The reaction vessel and contents were
ample 5. As a result of these operations, there was
agitated and heated under autogenous pressure to a tem 10 obtained a polyethyleneglycol 3,4-dihydro-6-phenyl-2H
perature of 120° and a pressure of 290 pounds per
1,3-benzoxazin-3-ylethyl monoether product as a water
square inch, and thereafter maintained at a temperature
of 120°-182° C. for 15 minutes. As a result of these
operations, there was obtained a polyethyleneglycol 6
soluble, viscous liquid having a refractive index n/D of
1.5330 at 25° C. and an average oxyethylene content‘,
of about 10 oxyethylene units per molecule.
chloro - 3,4 - dihydro-ZI-Ll,3-benzoxazin-3-ylethyl mono
EXAMPLE 16
ether product as a water soluble, viscous liquid having
an average oxyethylene content of about 40 oxyethylene
units per molecule.
Ethylene oxide (79.2 grams; 1.8 mole), 52.3 grams
(0.2 mole)v of 6-cyclohexyl-3,4-dihydro-2H-1,3-benzox
.
azine-S-ethanOl and 0.5 gram of sodium hydroxide were
EXAMPLE 10
Pentaethyleneglycol Z-aminoethyl monoether (65.3
grams; 0.23 mole) was reacted with 15 grams (0.5 mole)
of paraformaldehyde and 0.25 gram potassium hydroxide
20 reacted together in the manner as described in Example 5. ‘
As a result of these operations, there was obtained a
polyethyleneglycol 6 - cyclohexyl-3,4-dihydro-2H-1,3-ben
in 100 milliliters of methanol to produce an intermediate
product which was thereafter reacted with 37.5 grams
zoxazin-3-ylethyl monoether product as a water soluble,
viscous liquid having a refractive index n/D of 1.5089
reaction and methods of separation were exactly the same
as those described in Example 1. As a result ofvthese
operations, there was obtained a pentaethyleneglycol 6
hydro-ZH-l,3-benzoxazin-3-ylalkyl monoether compounds
25° C. and an average oxyethylene content of about
(0.25 mole) paratertiarybutylphenol. The conditions of 25 at
10 oxyethylene units per molecule.
tertiarybutyl-3,4-dihydro - 2H - 1,3 - benzoxazin-3-ylethyl
monoether product as a viscous liquid. This product
had a refractive index n/D of 1.5107 at 25° C., and was
soluble in acetone and ethanol.
EXAMPLE 11
In a similar manner, other polyalkyleneglycol 3,4-di
may be prepared of which the following are representa
30
tive.
’
-
'
A polypropyleneglycol 6-bromo - 3,4- dihydro-2H-1,3
benzoxazin-S-ylethyl monoether product containing an
average oxypropylene content of about 12 oxypropylene
units per molecule by reacting one mole of 6-bromo-3,4~
dihydro~2H¥1,3-benzoxazine - 3 - ethanol with about 11
3,4-dihydro-2H-1,3-benzoxazine-3-ethanol (35.8 grams;
0.2 mole), 79.2 grams (1.8 moles) of ethylene oxide and
moles of propylene oxide.
>
'
'
" i
v
'
'
A polyethyleneglycol 6,8-ldibrorno-3,4-dihydro-2H-1,3
0.5 gram of sodium hydroxide were reacted together sub
stantially as described in Example 5. As a result of these
tbenzoxazin-3-ylethyl monoether product containing an
average oxyethylene content of about 20 oxyethylene units
dihydro-ZH-1,3-benzoxazin-3-ylethyl monoether product 40 per molecule by reacting one mole of 6,8-dibromo-3,4
operations, there was obtained a‘polyethyleneglycol 3,4
dihydro-ZH-l,3-benzoxazine-3-ethanol with 19 moles of
as a viscous liquid having an index of refraction n/D
of 1.5079 at 25° C. and an average oxyethylene content
ethylene oxide.
3-ethanol and 0.5 gram of sodium hydroxide were re
15 moles of ethylene oxide.
-
~
'
A polyethylene glycol 6-bromo-3,4-dihydro-8-methyl
of about 10 oxyethylene units per molecule.
2H-l,3-benzox~azin-3-ylethyl monoether product contain
EXAMPLE 12
45 ing an average oxyethylene content of about 16 oxyethyl
ene units per molecule by reacting one mole of 6-bromol
Ethylene oxide (79.2 grams; 1.8 moles), 38.6 grams
3,4 - dihydro-S-methyl-ZH-1,3-benzoxazine-3-cthanol with
(0.2 mole) of 3,4-dihydro-6-methyl-2H-1,3-benzoxazine
' '
e‘ '
A polyalkyleneglycol 6 - bromo - 3,4 - dihydro-2H-1,3
acted together in substantially the manner as described
in Example 5. As a result of these operations, there 50 benzoxazin-3-ylethyl monoether product containing an
average oxyalkylene content of about 7 oxypropylene and
was obtained a polyethyleneglycol 3,4-'dihydro-6-methyl
8 oxyethyiene units per molecule by reacting onemole
21-1-1,3-benzoxazin-3-ylethyl monoether product as a water
of 6-bromo-3,4-dihydro-2H-l,3-benzoxazine-3-ethanol and
soluble, viscous liquid having a refractive index n/D of
1.5041 at 25° C. and an average oxyethylene content of
about 10 oxyethylene units per molecule.
successively with 7 moles each of propylene oxide and
55 ethylene oxide.
A polyethyleneglycol 6-bromo - 3,4 - dihydro-2H-1,3é
EXAMPLE 13
benzoxazin-3-ylethyl monoether product containing an
average oxyethylene content of about 40 oxyethylene units
Ethylene oxide (79.2 grams; 1.8 moles), 58.3 grams
per molecule by reacting one mole of 6-bromo-3,4-di
(0.2 mole) of 3,4-dihydr-o-6-(1,1,3,3-tetramethylbutyl),
2H-1,3-benzoxazine-3-ethanol and 0.5 gram sodium, hy 00 hydro-2H4,3-benzoxazina3-ethanol with 39 moles of
ethylene oxide;
,
'
droxide were reacted together as described in Example 5.
An octapropylene glycol 6-benzyl-3,4-dihydro-2H-1,3?
benzoxazin-3~ylisopropyl monoether by reacting together
propylene glycol 2~aminopropyl monoether, paraform
As a result of these operations, there was obtained a.
polyethyleneglycol 3,4-dihydro - 6 - (1,1,3,3 - tetramethyl
butyl)-2H-1,3-benzoxazin-3~ylethyl monoether product as
a viscous liquid having an index of refraction n/D of 65 aldehyde, and 4-benzylpheno1;
1.5000 and an average oxyethylene content of about 10
A poly-aliiyleneglycol 6 - tertiarybutyl-3,4-dihydro-2H
oxyethylene units per molecule.
EXAMPLE 14
1,3-benzoxazin-3-ylisopropyl monoether product con
taining an average oxyalkylene content of 4 oxyethylene
units and 4-oxypropylene units per molecule by reacting
Ethylene oxide (79.2 grams; 1.8 moles), 69.4 grams 70 together paraformaldehyde, 4-tertiarybutylphenol, and a
polyalkyleneglycol Z-aminoalkyl monoether containing an
3-ethanol, and 0.5 gram of potassium hydroxide were
average oxyalkylene content of '4 oxyethylene "units and
reacted together substantially as described in Example 6.
4 oxypropylene units per molecule;
'
‘
.
(0.2 mole) of 6-dodecyl-3,4-dihydro-2H-1,3-benzoxazine
As a result of these operations, there was obtained a poly
ethyleneglycol 6 - dodecy1-3 ,4-dihydro-2H-1,3-benzoxazin
A polypropylene glycol 6-hexadecyl-3,4-dihydro-2H
75
1,3-benzoxaziu—3-yl-?~methylethyl monoether containing
3,023,207
19 moles of propylene oxide;
8
of from about 1 to about 38 molecular proportions of
an average oxypropylene content of about 20‘ oxypropylene
units per molecule byvreacting one mole of 6-hexadecyl
3,4 - dihydro-2H-1,3-benzoxazine-3-;8-methylethanol with
total alkylene oxide, depending upon whether it is desired
to introduce from l'~38 alkylene oxide units in the mole
cule. The reaction between alkylene oxide and chloro
hydrin takes place smoothly at a temperature of about
’
A polyalkyleneglycol 5,6-dichloro-8-brorno-3,4-dil1yclr0
100° C. under atmospheric pressure.
21-1-1,3-benzoxazin-3-ylethyl monoether containing an
average oxyalkylene content of about 3 oxypropylene and
4 exyethylene units per molecule by reacting one mole of
In the second step of the method, the intermediate poly
alkyleneglycol chlorohydrin is caused to react with a
molecular excess of liquid ammonia or ammonium hy
5,6 - dichloro-B-bromo - 3,4-dihydro-2H-1,3-benzoxazine
droxide. The reaction takes place smoothly at about
10
3-ethanol with a mixture containing 3 moles of each of
100° C. and under an autogenous pressure of from about
ethylene oxide and propylene oxide.
50 to about 500 pounds per square inch. Upon comple
The preferred compounds of this invention are those
tion of the reaction the resulting reaction mixture may be
corresponding to the formula
concentrated by distillation under reduced pressure to
remove low boiling constituents and obtain the desired
starting material as a liquid residue.
The 3,4 - dihydro - 2H-1,3-benzoxazine-3-loweralkanol
starting materials as employed herein may be prepared
by causing two molecular proportions of formaldehyde,
C
II:
which may be in the form of a formaldehyde-yielding
substance such as paraformaldehyde, to react with one
in which Z represents
molecular proportion of ethanolamine Z-aminopropanol,
halogen halogen
|
I
l ’ halogen-Q1,
Halogen
hailogen
({JH
] .
halogen
l
halogen
I
or Laminoisopropanol to produce an intermediate form
aldehyde condensation product.
These products are
thereafter reacted with a suitable phenolic of the sort
described to obtain ‘the desired starting material. The
condition of reaction and methods of separation are all
as previously described for the type reaction.
—
3
The instant speci?cation and claims area continuation
30 in part of application Serial Number 700,544, ?led Decern—
and
L—
—
ber 4, 1957, now abandoned.
I claim:
1. A compound corresponding to the formula
‘ I
halogen
wherein L represents an alkyl radical containing from 1
to 16 carbon atoms, benzyl, phenyl, or cyclohexyl. The
new polyalkyleneglycol 3,4-dihydro-2H-1,3-benzoxazin-3
yl-alkyl monoethers of this invention are useful as para
siticides and herbicides. For such use the compounds
may be dispersed on inert ?nely divided solids and em
ployed as dusts. Also, such mixtures may be dispersed
in water with the aid of a Wetting agent, and the resulting
aqueous suspensions used as sprays. In other procedures,
the compounds may be employed in oil or other liquid
solvent and the resulting composition employed directly,
or as a component of oil-in-water or water-in-oil emulsions
to obtain preparations to be used as a spray or wash.
wherein each Y represents an alkylene radical contain
ing from 2 to 3 carbon atoms, inclusive, and having its
two valencies on adjacent carbon atoms, 11 represents an
integer from 6 to 40, inclusive, and R represents a mem
ber of the group consisting of o-phenylene and substituted
o-phenylene in which the substituents are selected from
the group consisting of chlorine, bromine, phenyl, benzyl,
In a representative operation a seedbed planted with the
cyclohexyl, and alkyl containing from 1 to 16 carbon
seeds of canary gras was saturated with an aqueous com
atoms.
position comprising as sole toxicant 100 parts by weight
2. The polyalkyleneglycol 6—chloro—3,4-dihydro-2I-I-1,3
of the pentaethyleneglycol 6-tertiarybutyl-3,4-dihydro-2H
benzoxazin-Fl-ylalkyl monoether corresponding to the
1,3-benzoxazin-3-ylethyl monoether per million parts of
formula
ultimate mixture. This treatment resulted in a 93 percent
0
CH:
control of the growth of the germinant seeds and emerging
55
seedlings of the canary grass.
The polyalkyleneglycol aminoalkyl monoethers em
ployed as starting materials in accordance with the teach
ings of the present invention may be prepared by known
wherein each Y represents an alkylene radical containing
procedures. In one such procedure, ethylene oxide or
propylene oxide is caused to react with an alkylene chloro
hydrin such as ethylene chlorohydrin 2-chloropropanol or
2-chloroisopropanol in the presence of an aluminum oxide
catalyst to yieldan intermediate polyalkyleneglycol chloro
hydrin product. This intermediate is thereafter caused
to react with ammonia to obtain the desired polyalkylene
from 2 to 3 carbon ‘atoms inclusive, and having its two
valencies on adjacent carbon atoms, and n represents an
integer from 6 to 40 inclusive.
3. The polyalkyleneglycol 5,6,8-trichloro-3,4-dihydro
21-1-1,3-benzoxazin-3-ylalkyl monoether corresponding to
the formula
p1
glycol aminoalkyl monoether product. In the ?rst step
of the method, the average number of oxyalkylene units
introduced into the molecule is somewhat dependent upon
0\
the conditions under which the reactants are brought to
gether, and primarily dependent upon the molar ratio 70
of employed alkylene chlorohydrin reactant and alkylene
01
\C
I
Hz
re
N—(Y—O~) n-H
01
oxide. Thus one molecular proportion of the chloro
hydrin reactant is caused to react with ethylene oxide or
wherein each Y represents an alkylene radical containing
propylene oxide, or a mixture thereof, or successively
with each of ethylene oxide or propylene oxide in the ratio 75 from 2 to 3 carbon atoms, inclusive, and having its two
3,023,207’
1'0
valencies on adjacent carbon atoms, and n represents an
dro-2H-l,3-'benz‘oxazin-3-yla1kyl monoether corresponding
integer from 6 to 40, inclusive.
to the formula
’
4. The polyalkyleneglycol 6, 8-dichloro-3,4-dihydro-2H~
1,3-benzoXazin-3-y1alky1 monoether corresponding to the
formula
'
wherein each Y represents an alkylene radical containing
from 2 to 3 carbon atoms, inclusive, and having its two
valencies on adjacent carbon atoms, and n represents an
wherein each Y represents an alkylene radical containing
from 2 to 3 carbon atoms, inclusive, and having its two
valencies on adjacent carbon atoms, and n represents an 15
integer from 6 to 40, inclusive.
5. The polyalkyleneglycol 6-chloro-8-methyl-3,4-dihy
Au
integer from 6 to 40, inclusive.
References Cited in the ?le of this patent
UNITED STATES PATENTS
> 2,571,985
Carnes _______________ _._ Oct. 16, 1951
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3,023,207
February 27, 1962
Raymond H. Rigterink
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
Column 3, lines 14 to 19, the formula should appear as
shown below instead of as in the patent:
C1
0
\CH
I 2
C/
Cl
‘
H
c 1
2
Signed and sealed this 24th day of July 1962.
(SEAL)
Attest:
ERNEST W. SWIDER -
DAVID L. LADD
Attesting Officer
Commissioner of Patents
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