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Патент USA US3100801

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United States Patent 0
1 F‘.
Patented Aug. 13, 1963
Walter B. Trapp and James D. Doedens, Midland, Mich”
assignors to The Dow Chemical Company, Midland,
Mich, a corporation of Delaware
No Drawing. Filed Apr. 4, 1960, Ser. No. 19,507
5 Claims. (Cl. 260-488)
This invention concerns ar-poly(hydroxymethyl)di
phenyl ethers and their method of preparation. More;
particularly, ‘it concerns those ar-poly(hydroxymethyl)di—.
phenyl ethers (hereinafter ar-PHMDPE’s) having in ex
tude exists as to the proportions of materials. The alkali
metal carbonate or bicarbonate, for example, is advan
tageously used in amount up to 10 percent excess of
stoichiometric requirements for hydrolyzing the halo
methyl groups. For 100 parts of 4,4’-di(halomethyl)di
phenyl ether, for example, :irom 40 to 46 weight parts
sodium carbonate or equivalent alkali metal. carbonate
bicarbonate is advantageously used together with 160
300 parts of water and 700 to 2000 parts of acetone
equivalent solvent, as set forth above.
of ,
. Another’ method for making the ar-PHMDPE’s of this
invention is to form an emulsion of ar-poly(halomethyl)
diphenyl ether in aqueous alkali metal hydroxide solu
cess of one and up to 4 hydroxymethyl groups per di
phenyl oxide moiety wherein up to 2 hydroxymethyl 15 tron using an oil-in-Water emulsifying agent such as the
Well-known alkyl sulfonates, alkyl aryl sulfonates, polys
groups are on one aromatic nucleus. The invention fur
ther concerns a method for making such ar~PHMDPEs .
ether non-ionics, alkyl sulfates ‘and sulfonated alkyl aryl
by reacting corresponding ar-poly(CH2X)diphenyl others
ethers,‘ advantageously sulfonated dodecyldiphenyl ethers,
invention have the formula: .
0.5 to 2 weight percent of emulsifying agent, ar-poly
(halomethyl)diphenyl ether basis, and from one weight
and heating the resulting mixture with agitation at atmos
wherein X is one of acetoxy, bromine and chlorine to
hydrolyze the X groups to corresponding alcoholic OH 20. pheric pressure or in a closed system at about 80° to
100° C. ‘for a time suf?cient to hydrolyze the bromine or
groups and recovering the ar-PHMDPE.
advantageously for about 5 hours. From about
The new, useful and unobvious compounds of this
part of ar-poly(halomethyl)diphenyl ether to 4 to 50
25 parts Water is advantageously used.
wherein n is a quantity'between 0 and 2 and the sum of .
n and n’ is in excess of one and up to Zland includes
2,4’-dimethyloldiphenyl ether, 4,4’-dimethyloldiphenyl
Product purity in
creases with increasing water content of the emulsion, the
upper limit of which is purely economic. A Volhard
halide analysis suffices to determine when hydrolysis is
1 complete
or substantially complete.
The hydrolysis re
ether, trimethyloldiphenyl ether and tetramethyloldiphenyl 30 action involves a stoichiometric equivalent of alkali metal
ether and mixtures thereof. They are useful in making
hydroxide advantageously present in up to 10 percent
alkyd and polyester resins following usual procedures in
place of polyhydric alcohols conventionally used. The
It is not essential that the ar-poly(CI{ZX)diphenyl
V4,4’~dimethyloldiphenyl ether is a nematocide.
The ar-PHMDPE’s of this invention are made by hy
ethers used as reactants in this invention be pure com
35 pounds. On the contrary, commercial mixtures are most
drolyzing the X of the CHZX groups of the corresponding
attractive by reason of their readier availability and lower
ar-poly(CI-I‘2X)dipheny1 ethers wherein X has the mean
ing indicated above. The hydrolysis can be carried out in
The following examples describe- completely speci?c
embodiments of the invention claimed and the best mode
various ways. The novel ar-poly(acetoxymethyl) inter
mediates, for example, can be hydrolyzed by heating their 40 contemplated by the inventors for practicing their claimed
‘ invention.
solution in a lower monohydric alcohol, e.g., methanol,
' ethanol, propanol, or butanol or a suspension of such an
Example 1
intermediate in water with excess aqueous alkali metal
Aquantity of 500 grams (1.875 moles) of 4,4'-dichloro
hydroxide over that required by the acetoxymethyl groups
methyDdiphenyl ether, 328 grams (4.0 moles) of sodium
to a temperature within the range of about 75 °—l00° C. 45
acetate and 1200 ml. of acetic acid was combined and
' heated to re?ux with stirring for eight hours. The cooled
hydrolyze oil the acetoxy groups and to replace the latter
mixture was ?ltered to remove sodium chloride and the
with alcoholic OH groups. A melting point test of the
?ltrate was heated to 90° C. under water aspirator vacuum
product sun-lees to determine when this reaction has been
50 to remove the acetic acid solvent. The residual crude
for a time su?icient (generally up to about two hours) to
completed or substantially completed. The resulting mix
ture is‘ diluted with water, ?ltered oii, washed by reslurry- ‘
ing with water, and dried, advantageously in a desiccator
product was puri?ed by dissolving in chlorobenzene and
extracting the resulting solution with water. The solution
was then stripped of solvent and traces of low boilers by
or even in the open air.
heating to 180° C. at one mm. Hg pressure. The residual
The halomethyl intermediates ‘for the ar-PHMDPE’S
diacetate product melted at 45° C.
can be hydrolyzed to the latter by re?uxing their solutions 55
Analysis.—Calcd. for. C18H18O5: C, 68.8; H, 5.76.
in acetone, methylethyl ketone, dioxane or t-butyl alcohol,
with excess aqueous alkali metal carbonate or bicarbonate \
over that required by the halomethyl groups at a tempera
Found: C, 68.68; H, 5.99.
Example 2
p,p'-Oxydibenzyl alcohol ‘diacetate (100 grams, 0.318
ture between about 60°—65° C. for a time sui?cient to
hydrolyze the bromine or chlorine and replace it with 60 mole), ‘was dissolved in 100. ml. of 95 percentethanol.
alcoholic hydroxyl. Hydrolysis time generally requires
This solution was combined with 240 grams of 16.7 per
cent NaOH in water (1.0 mole) in a one-liter flask and
at least 5 hours and usually not more than 6 hours, and.
can be determined by an analytic test for halogen on a
heated to 85° C. with agitation. An exothermic effect
portion of water washed product.
occurred between 25° and 55° C.
The solvent is then ;
The mixture was a
removed and the product is washed free of salt impurities, 65 semi-solid between 50° and 75 ° C. A clear solution existed
, advantageously by distillatively stripping off the solvent
while simultaneously adding water to the reacted mixture
at a rate substantially equal to that of the solvent removal.
about 75° C. After 45 min. at 85° C., the mixture was
cooled and diluted with 100 ml. water. The solid prod
uct was separated by ?ltration and reslurried and washed
with water to give 69.5 ‘grams (95 percent) of p,p»’~oxy
Thereby product ar-PHMDPE is precipitated and is there
after ?ltered, washed (advantageously by reslurrying with 70 dibenzyl alcohol, M.P‘. l32°-134.5° C.
Analysis.—~Calcd. > for CHHMOB: C, 73.l; H, 6.13.
water and re?ltering) and dried.
In the solvent method just described, considerable. lati
Found: C, 72.92; H, 6.23.
Example 3
A quantity of 307 grams of crude 4,4'-oxydibenzyl
containing 2—mono(methylol)diphenyl ether, 4-mono
ether, 2,4’~di(methylol)diphenyl
ether, 4,4’-di(methylolydiphenyl ether, tri(methylol)di
. (methylol)diphenyl
alcohol diacetate, freezing point 356° C., was, agitated
with aqueous sodium hydroxide solution (125 grams sodi
'u1rn‘ hydroxide in 500‘ ml. water) and the mixture was
- maintained at 106° C. for two hours.
phenyl ether and tetra(methylol)diphenyl ether corre
sponding substantially to that of the starting mixture
of chloromethyld-iphenyl ethers.
The resulting
product was ?ltered, reslur'ried and washed with water
and dried to give an ‘88 percent yield of 4,4'-oxydibenzyl
alcohol, M.P. 130°-133° C.
Example 7
. Example 4
The product was a mixture of methyloldiphenyl ethers
A quantity of 534 grams arapoly (chloromethyDdiphen
yl ether having the following composition:
A solution of 100 parts by weight of 4,4’-di(chloro
methyDdiphenyl ether in 800 parts of acetone was com
Mole percent
Z-mono (chloromethyDdiphenyl ether _________ __
bined with a solution of 42 parts of NlaQCO3 in 200 parts
4-mono(chloromethyl)diphenyl ethere _______ __
of Water and heated at reflux at atmospheric pressure with 15 2,4’-di(chloro-methyl)diphenyl ether.‘ ________ __
agitation for six hours. The acetone was then stripped
4,4'adi(chlorornethyl)diphenyl ether ________ __
off by distillation while simultaneously adding water to
Tri(chloromethyl)diphenyl ether ___________ __
the mixture continuously at a rate equal to the rate of
Tetna(chloromethyl)diphenyl ether __________ __
acetone removal. The product 4,4’-oxydibenzyl alcohol
- precipitated during this operation and was ?ltered, washed
with water, again ?ltered and ?nally dried to give a prod
uct melting between 128° and 134° C.
‘Other solvents that can be used in this hydrolysis in
was added to
162 g. water
540 g. glacial acetic acid
clude methylethyl lcetone, dioxane and tdbutyl alcohol.
in a 3-liter ?ask equipped with a stirrer, condenser and
. Alkali metal bicarbonate can be substituted for edkali
25° C. to 115° C. Acetic acid and water were distilled
ous 50 percent sodium hydroxide, 1.5 ml. aqueous 30
mixture was heated one hour at 100° C. after complete
Primary and secondary alcohols are unsatisfactory because 25 fractionating column. Sodium hydroxide (182 g.) was
added slowly thereto while the temperature rose from
of a strong tendency toward ether formation.
off during the reaction (approximately 1% hr.). Dis
metal carbonate in the hydrolysis.
tillation was stopped when the pot temperature reached
Example 5
Hg pressure. The reaction mixture
3.0 160“ C. at 20
was cooled to 100° C. and 500 g. waiter was added. A
A quantity of 50 grams of 4,4'-di(chloromethyl)di
quantity 0st 364 g. aqueous 50 percent sodium hydroxide
phenyl ether, M.P. 64°~65° C., was emulsi?ed by stir
was added slowly to effect saponi?cation. The reaction
ring into an aqueous solution consisting of 32 grams aque
percent commercial sulfon-ated dodecyldiphenyl ether and 35 addition of the caustic. It was then cooled to room-ten»
484 ml. water. The reaction temperature was maintained
at 85°-95° C. and at atmospheric pressure for seven
perature and washed with water until neutral. The
product at this time was still a liquid. After separation,
the organic phase was dried by azeotropic distillation
with'toluene. vThe toluene was distilled oil to a pot tem~
in ‘98 percent yield by ?ltering, slurrying and washing
Hg. The ?nal product
with water, ?ltering again and drying. Its melting point 40 perature of 100° C. at 20
hours with stirring. The resulting product was recovered
was a ‘clear, viscous, light-colored liquid that solidi?ed
on cooling. This product had a freezing point of 61°
Example 6
63° C. and weighed 447 1g. for an 86.2 percent yield
based on OH present. Analysis of the product showed
A quantity of 534 grams ar-poly(chloromethyl)diphen
yl ether having the following composition:
45 11.16 percent OH and 0.056 percent chlorine. The mix
ture of methyloldiphenyl ethers present had a distribution
Mole percent
corresponding substantially to that of the starting mix
2-rnono(chloromethyl)diphenyl ether __________ __ 0.25
ture of chloromethyidiphenyl ethers.
was 128°-130° C.
4-mono(chloromethyl)diphenyl ether __________ __
2,4'-di(chloromethyl)diphenyl ether ___________ __
4,4'-di-(chloromethyl)diphenyl ether ____________ __
Tri(chloromethyl)diphenyl ether ______________ __
Tetra(chloromethyl)_diphenyl ether ____________ __
wlas added to
540 ‘g. glacial acetic acid
162 g. water
185 g. 97.1 percent pure sodium hydroxide
in a glass reactor equipped with a'mechanical agitator,
Example 8
Six ml. of a suspension of rootknot nematodes
(Meloidogyne spp.) in aerated distilled water buttered to
pH 7.0 with 1/100 molar potassium phosphate were
added to 3 dram vials. Three replicates were prepared
55 for each chemical treatment, checks containing acetone
and checks not containing acetone. A quantity of one
'gram of 4,4'-oxydibenzyl alcohol was dissolved in 50 ml.
acetone and 2.5 ml. of this solution was dissolved in
200 ml. of distilled water. Four ml. of this ?nal com
thermometer and distillation column. The mixture was 60 position was added to the 6 ml. of nematode suspension
to give a concentration of 100 ppm. of the oxydibenzyl
heated with stirring and the reaction began at 112°-115°'
alcohol. Containers were capped. After incubation for
C. Acetic acid and water were distilled off as the reac
tion commenced and then ?nally removed completely up
to 150° C./2 cm. Hg absolute pressure. After cooling
six days at 80° F., the percent mortality was 73 percent.
For the acetone check, mortality was 10 percent and for
to 100° C., 500 ml. water was added, the mixture was 65 the check not containing ‘acetone, about 5 percent.
- heated to re?ux, and aqueous 50 percent sodium hydroxide
.What is claimed is:
was added slowly to hydrolyze the acetate groups to
1. ar-Acetoxymethyldiphenyl ethers having from 1 to 4
methylol groups. Heating was continued an additional
acetoxymethyl groups per molecule, up to 2 of which
hour after all of the sodium hydroxide had been added.
are on one benzene nucleus.
The‘ reaction mixture was cooled to 25 °-30° C. and ?l 70
2. Method for making ar-poly(hydroxymethyl)diphenyla
tered. The crystalline product was washed with water
ethers having up to 4 hydroxymethyl groups per mole
until neutral and tree of chloride, and then dried. A
by hydrolysis at a temperature between about 75° and
quantity of 446 g. product was recovered for a 94.6 per
110° C. of ar-poly(acetoxymethyl)diphenyl ethers having
cent yield. Freezing point of the mixed methylols was
up to 4 acetoxy groups per mole, up to 2 of which are
110° C.
on one benzene nucleus with a stoichiometric excess of
an alkali metal hydroxide for a time su?icient to displace
and t-butyl ether, for a time su?icient to displace chloro-v
acetoxymethyl groups and to replace them with hydroxyl
groups and separating the ar-poly(hydroxymethyl)di
phenyl ether product from the reaction medium.
methyl groups and replace them with hydroxyl groups
and recovering ar-poly(hydroxymethyl)diphenyl ether
3. Method of claim 2 wherein the ar-poly(acetoxy
methyl)diphenyl ether is in solution in a lower mono
hydric alcohol having from 1 to 4 carbon atoms.
4. Method of claim 2 wherein the ar-poly(acetoxy
methyl)diphenyl ether is suspended in water.
5. Method of making ar-poly(hydroxymethyl)diphenyl 10
ethers having up to 4 hydroxymethyl groups per mole
by hydrolysis at a temperature between about 60° ‘and
100° C. of ar-poly(ha1omethy1)diphenyl ethers having
up to 4 halomethyl groups per mole, halo being one
of chloro and bromo, up to 2 of which halomethyl groups
are on one benzene nucleus with a stoichiometric excess
of a member of the group of alkali metal carbonates and
alkali metal bicarbonates, wherein said ar-poly(halo
References Cited in. the ?le of this patent
Coleman ____________ __ Sept. 20, 1938
Head _______________ __ May 19, 1953
Bader __________ _‘______ Feb‘. 4, 1958
2,963,379 .
Doedens ____________ __ Nov. 3, 1959
Kaupp et al. _________ __ Dec. 6, 1960
.Karrer: “Organic Chemistry,” 4th Edition, Elsevier
Pub. Co., Inc., New York, 1950, page 82.
Wagner et al.: “Synthetic Organic Chemistry,” Wiley
and Sons, Inc., New York, 1953, pages 169 to 171.
Fieser et al.: “Organic Chemistry,” 3rd Edition, Rein
group consisting of acetone, methylethyl 'etone, dioxane 20 hold Pub. Corp., New York, 1956, page 178.
methyDdiphenyl ether is in solution in a member of the
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