United States Patent Office 2,859,253

Patented Nov. 4, 1958

2
being between about 3.5 to 4.5:1) is heated to a tempera
ture varying between about 58-63 C. The reaction is
2,859,253 carried out by passing gaseous hydrogen chloride into
PROCESS FOR THE CONTINUOUS PREPARA. the reaction mixture. The addition of the hydrogen chlo
TION OF BENZYL CHLORIDE ride gas to the mixture should be effected rapidly; that is,
in as short a time as practicable. This period preferably
John E. Snow, Hasbrouck Heights, N. J., assignor to should not exceed 1/2 hours.
Heyden Newport Chemical Corporation, a corpora The reaction mixture is then cooled, thereby forming
tion of Delaware two layers. The upper layer containing the benzyl chlo
No Drawing. Application October 19, 1955 ride is removed while the lower aqueous catalyst-con
Serial No. 541,523 taining layer is allowed to remain in the reaction vessel.
4 Claims. (C. 260-651) Benzene is added to this lower layer and this is followed
by removing the water present in this benzene-zinc chlo
ride mixture as a benzene-water azeotrope. To this de
This invention relates to a process for producing benzyl hydrated zinc chloride mixture are added substantially
chloride and more specifically, to a continuous process the same quantity of benzene, formaldehyde and water,
for the production of benzyl chloride by the chlorometh and the chloromethylation process is repeated once again.
ylation of benzene and to improvements in the process of The upper layer which has been drawn off from the
chloromethylating benzene. reactor is washed with water, then with a dilute solution
This application is a continuation-in-part of my co 20 of alkaline bicarbonate followed by another wash with
pending application Serial No. 300,758, filed July 24, water. The product is then dried over calcium chloride
1952, now abandoned, which in turn is a continuation-in or some other suitable dehydrating agent and is then
part of my application Serial No. 213,047, filed Febru vacuum distilled at 60 mm. pressure. The distillate be
ary 27, 1951, now abandoned, and application Serial No. 25 tween 96-98 C. is collected to obtain a benzyl chlo
ride product of high purity.
64,249, filed December 8, 1948, now abandoned.
It has now been discovered that benzyl chloride can In this process, it has been found that the initial mole
be continuously prepared by reacting benzene together ratio of zinc chloride to water will directly affect the final
with aqueous formaldehyde in the presence of zinc chlo yield of benzyl chloride obtained. For example, if the
ride catalyst. The benzyl chloride-containing layer is 30 initial mole ratio, that is, water to zinc chloride at the
beginning of the reaction, is within the limits of 3.5 to
removed from the reaction mixture and then the aqueous 4.5:1 respectively, higher yields of benzyl chloride are
catalyst-containing layer remaining in the reactor is de
hydrated and the cycle for the production of benzyl chlo obtained. For example, yields of benzyl chloride of 76%
ride is repeated by the addition of benzene and formalde or more, based on the amount of formaldehyde charged,
hyde to the catalyst in the reactor. The efficiency of can be obtained. By using a preferred ratio of water to
this process is illustrated by the low losses and consistently 35 zinc chloride, surprisingly the change in the mole ratio
of zinc chloride to water during the reaction is mini
high yields obtained.
It also has been discovered that the initial mole ratio mized, and at the completion of the reaction does not,
of water to zinc chloride materially influences the yield. as a rule, exceed about 6:1. Any variance from the
Surprisingly, if this ratio is in the hereinafter defined 40 preferred initial ratio, and especially if a mole ratio be
low 3:1 is used, low yields are obtained. If a ratio is
range, the yield is not only higher than when relatively
more water is present but the yield is higher than when used which is higher than that indicated, the ratio at
less or even no water is present. In other words, while the end of the reaction will be undesirably high and the
the presence of a small amount of water apparently re yield likewise will be perceptibly lower. If the zinc con
centration is low, complete reaction with the formalde
duces the yield below that obtained under anhydrous con hyde will not be effected and in addition, undesirable side
ditions, the presence of the specified amount of water in reactions may produce polymeric compounds, of form
creases the yield above that obtained under anhydrous
conditions. aldehyde and benzene.
A highly desirable feature of this process involves de As used herein, the term "substantially methanol-free
formaldehyde' refers to aqueous formaldehyde not con
hydration of the catalyst in the reaction vessel at a tem 50 taining
perature below 100° C. without the need for removal of more than 1% by weight of methanol. Aqueous
the catalyst from the reaction vessel or the necessity for formaldehyde of different concentrations may be used.
measuring the catalyst concentration. The necessity for However, the amount of water present in the aqueous
imeasuring the catalyst is overcome by the fact that there formaldehyde and the added water, if any, must be taken
is substantially no loss of catalyst under these condi into consideration when calculating the mole ratio of wa
tions. ter to Zinc chloride. The expression “aqueous formalde
It also has been discovered that the efficiency of the hyde" is not intended to include paraformaldehyde which
process of chloromethylating benzene in the presence of would be an unduly expensive source of formaldehyde.
aqueous formaldehyde and a catalyst such as zinc chlo By removing the benzyl chloride layer and then adding
ride is greatly increased by using methanol-free aqueous the chloromethylation reactants to the dehydrated zinc
formaldehyde. Normally and unless stated otherwise, 60 chloride in the reactor, the chloromethylation process
commercial N. F. aqueous formaldehyde contains about is continuous in nature. -
6% or more methanol. Methanol-free aqueous formalde While this invention can be carried out in various
hyde normally is used only when required as it has to be ways, for the purpose of illustration I have described
carefully handled and stored and is more expensive. hereinafter only certain examples of the procedure for
Surprisingly, it has been discovered that if methanol-free this purpose. All percentages are by weight. The yield
formaldehyde containing not more than 1% methanol of benzyl chloride is based on the amount of formalde
is used, there is an unexpected increase in the production hyde charged.
of benzyl chloride. EXAMPLE I
In a more specific embodiment of this invention, a mix 70 Three hundred parts (3.85 moles) of benzene, 81 parts
ture containing benzene, an aqueous solution of formalde (1 mole) of 37% substantially methanol-free formalde
hyde containing about 37% by weight of formaldehyde, hyde, and 100 parts (0.74 mole) of pulverized fused.
and zinc chloride (the water to zinc chloride mole ratio
 2,859,253
3 4
U. S. P. zinc chloride were charged into a one-liter, Variation in yield of benzyl chloride with change in the
three-neck, round-bottom flask equipped with theromom molar ratio of water to zinc chloride at end of the
eter, air-driven Hershberg Nichrome wire stirrer, and reaction 1
gas inlet tube. The ingredients were stirred and then
heated to 60° C. before the addition of gaseous HCl was Analysis of Calculated Molar
begun. The temperature was held at 60°C. while HCl Grams Percent
Benzyl Chloride 2 Ratio of Water to
Zinc Chloride
was passed over the surface of the rapidly stirred charge Zinc Yied Grams
for 1% hours to effect chloromethylation of the benzene. Chloride
Used
Benzyl
Chloride Percent. Percent .
Residue
At Start At End
The reaction mixture was cooled to 27 C. and the layers Cl ECHO of of
separated. The upper layer was washed with water, 5% IO Reaction. Reaction ,
sodium bicarbonate solution, and again with water and
then dried over CaCl2. It was then stripped of benzene 68.8 28.
80-------- { S: 3:3; None
NE 6.0
} 4.82: to.
6.52:
and vacuum distilled to yield at 96-98 C./60 mm.,
99.9 parts of benzyl chloride. This amounts to 78.9% 90--------Kf 80.:4 28.02
SS, NE --

None
O8.
;1.5 : 4.30:1. 5.80:1
of the theoretical yield. Chlorine percentage on analysis it}).------ 8.6 28.0 None 9.7 3.85: 5.20:1
was 27.96% (theory 28.1%).
To the lower layer was added about 1 mole of ben 110-------
Si as S.
22, 27.4 0.03
- 3
13.
g; } 3.5: ; 4.3:
2.

zene. The mixture was heated under reflux until the

zinc chloride was substantially dry. Ninety three ml. of
water were collected in a modified Dean and Stark mois 20
r: ; ; , . None.
150-------K 57.4- 28.1
27. NOl .. .
14. 7.
1.9 } a la
.
3 Asi
3.48:1
ture trap. The benzene can be reused. The addition of All runs on one mole 37% formaldehyde basis. . .
benzene is highly desirable as the benzene aids in remov 2 Theoretical for benzyl chloride 28.1% Cl; 0.0%HCHO.
ing the water. It was possible to remove substantially As indicated, only a single reactor has been used in
all of the water at a temperature below the boiling point
of water, that is, about 80 C. Without the benzene, it 25 this process for the continuous production of benzyl
is necessary to heat the mixture to a much higher tem chloride. Since the catalyst regeneration step is more
perature at which the small amount of organic residue time-consuming than the chloromethylation step it is
apparently decomposes and contaminates the catalyst. It quite possible, however, to use two or more reactors
was found in practice that better results were obtained thereby staggering the cycles in this proposed modifica
when benzene was added to the aqueous catalyst layer. 30 tion.
To the dehydrated benzene-zinc chloride mixture was As previously indicated, it is highly desirable that
added 300 parts (3.85 moles) of benzene and 81 parts benzene be added to the aqueous zinc chloride layer
(1 mole) of 37% methanol-free formaldehyde. The in the reactor after removal of the benzyl chloride and
chloromethylation reaction was carried out as described before dehydrating the catalyst. The amount of benzene
above. This time the yield was 103.7 parts of benzyl may be varied widely although excellent results have
chloride, 81.8% of theory. Chlorine percentage on been obtained when the number of moles of added ben
analysis was 27.84% (theory 28.1%). zene are about equal to the number of moles of zinc
Once again benzene was added to the aqueous layer, chloride. With benzene added, it is possible to effect de
and the mixture was refluxed until 96 ml. of water had hydration by heating the mixture in the reactor to a
been collected in the water trap. 40 temperature below 100° C. to remove the water as a
The regenerated zinc chloride was used in a third benzene-water azeotrope; whereas, zinc chloride is cus
chloromethylation run. The yield of benzyl chloride was tomarily completely dehydrated by heating the zinc chlo
99.4 parts (78.8% of theory). Chlorine percentage on ride to its melting point to effect fusion. Zinc chloride
analysis was 27.72%. is very hygroscopic. During dehydration, the added ben
The above runs were repeated with the following Zene is removed along with the water and the benzene
results: can be separated and reused. While it would not be
First chloromethylation-99.3 parts of benzyl chloride necessary to substantially completely dehydrate the cata
(78.4% of theory). Chlorine analysis 27.86%. lyst if formalin containing a higher percentage of formal
dehyde were added to the regenerated catalyst, this would:
Second chloromethylation-101.8 parts of benzyl chloride ; in
(80.5% of theory). Chlorine analysis 27.92%. practice involve a number of difficulties. One difficulty
would be that solutions of different aldehyde concentra
Third chloromethylation-100.9 parts of benzyl chloride tions would have to be prepared and used. In addition,
(79.6% of theory). Chlorine analysis 27.80%. the residual water should be measured to assure the
proper ratio of water to zinc chloride in the reaction
Additional experiments were performed to determine 5 5 mixture.
the correlation between the initial concentration of ben Accordingly, it is quite desirable to dehydrate
zene and the yield of benzyl chloride obtained. The re substantially completely the zinc chloride in the reactor
sults are as follows (the runs were made using 100 before adding additional water, formaldehyde and ben
ZCC
grams of zinc chloride and 1.0 mole 37% methanol-free
formaldehyde): 60 EXAMPLE II
Four hundred parts (5.14 moles) of reagent grade.
Percent Yield benzene, 100 parts (0.735 mole) of pulverized zinc chlo
Quantity of Benzene Benzyl ride, and 81 parts (1 mole) of 37.1% formaldehyde,
Chloride were placed in a flask equipped with a stirrer and a
reflux condenser. The mixture was stirred and heated
to about 60° C. and gaseous hydrogen chloride was
bubbled into the reaction mixture at an average rate of:
approximately 2 moles per hour. The temperature of
the reaction mixture was maintained at about 60° C. by
cooling. The reaction was substantially complete at the
end of one hour, although the addition of hydrogen chlo-.
To illustrate the fact that the most satisfactory yields ride gas with stirring was continued for an additional
are obtained in this reaction when the water is present at fifteen minutes. The reaction mixture was cooled to
the beginning and at the end of the reaction in certain 25 C. The lower aqeous zinc chloride layer was re
definite ratios to the amount of zinc chloride used, the 5 moved. The upper layer containing benzene, benzyl .
following experiments were performed. chloride and other reaction products, was washed with
 2,859,258
5 6
water, then with a 5% sodium bicarbonate solution and chloromethylating benzene to form benzyl chloride in a
again with water. The washed benzene solution was reaction vessel by passing gaseous hydrogen chloride
dried and 276.1 parts of benzene were removed by dis into a quantity of aqueous reaction mixture containing
tillation at atmospheric pressure. Vacuum distillation a quantity of benzene and substantially methanol-free
of the residue gave 102 parts of benzyl chloride which aqueous formaldehyde in the presence of a quantity of
was 81.5% of the theoretical amount. zinc chloride, the initial molar ratio of water to zinc
EXAMPLE I
chloride in the reaction mixture being about 4:1, cool
ing the mixture and allowing the mixture to separate into
In this comparative example, the procedure was the upper and lower layers in the reaction vessel, remov
same as described in Example II except that the aqueous O ing the upper layer containing benzyl chloride while al
formaldehyde contained 7.2% methanol. The yield was lowing the catalyst-containing aqueous lower layer to
only 70.7%. remain in the reaction vessel, separating benzyl chloride
Some of the features of the present invention may from the upper layer, regenerating the catalyst in the
be employed without others. However, best results are aqueous lower layer remaining in the reaction vessel by
obtained when all of the features are combined to form 5 adding benzene to the reaction vessel followed by sub
the optimum process. stantially completely dehydrating the resultant mixture
I claim: by azeotropic distillation at atmospheric pressure and
1. In a process for preparing benzyl chloride in high at a temperature below 100 C., adding substantially
yield, the steps comprising chloromethylating benzene the same quantity of benzene, and methanol-free aque
to form benzyl chloride in a reaction vessel by passing 20 ous formaldehyde to the regenerated catalyst in the re
gaseous hydrogen chloride into an aqueous reaction mix action vessel to form substantially the same quantity of
ture containing benzene and substantially methanol-free aqueous reaction mixture containing. Substantially the
aqueous formaldehyde in the presence of zinc chloride, same quantity of zinc chloride, the molar ratio of water
the initial molar ratio of water to zinc chloride in the to zinc chloride being about 4:1, and then repeating the
reaction mixture being between 3.5 to 4.5:1, cooling the 25 chloromethylating step to obtain again substantially the
mixture, removing the upper layer of the mixture con same quantity of benzyl chloride in high yield.
taining benzyl chloride while allowing the catalyst-con 4. In a process for continuously preparing benzyl
taining aqueous lower layer to remain in the reaction chloride in substantially pure form and in high yield, the
vessel, separating benzyl chloride from the removed steps which comprise reacting at a temperature of about
upper layer, regenerating the catalyst in the aqueous 30 58-63 C, a mixture containing a quantity of benzene
lower layer remaining in the reaction vessel by adding and a quantity of substantially methanol-free aqueous
benzene to the layer followed by substantially completely formaldehyde in the presence of a quantity of zinc
dehydrating the resultant mixture by azeotropic distill chloride, the molar ratio of water to zinc chloride in the
lation at atmospheric pressure and at a temperature 35 reaction mixture being between 3.5 to 4.5:1, passing
below 100 C., adding benzene, water and such an alde gaseous hydrogen chloride into the reaction mixture,
cooling said mixture, removing the upper layer of said
hyde to the regenerated catalyst in the reaction vessel, reaction
the molar ratio of water to zinc chloride in the reaction mixture containing benzyl chloride wihle allow
mixture varying between 3.5 to 4.5:1, and then repeat in ing the catalyst-containing aqueous lower layer to remain
ing the chloromethylating step to obtain an additional 40 the reaction vessel, washing said layer containing
quantity of benzyl chloride. benzyl chloride with water and an alkali-bicarbonate solu
2. In a process for continuously preparing a quantity tion, distilling the resulting solution at about 60 mm. pres
of benzyl chloride in high yield, the steps comprising sure, collecting the portion boiling off between 96-98
chloromethylating benzene to form benzyl chloride in a C. to obtain a quantity of substantially pure benzyl
chloride, adding benzene to said lower layer remaining
reaction vessel by passing gaseous hydrogen chloride into 45 in
a quantity of aqueous reaction mixture containing a ingsaid the
reaction vessel, substantially completely dehydrat
benzene-zinc chloride mixture by azeotropic dis
quantity of benzene and substantially methanol-free
aqueous formaldehyde in the presence of a quantity of tillation at temperature below 100 C. to obtain substan
tially the same quantity of anhydrous zinc chloride and
zinc chloride, the initial molar ratio of water to zinc then adding thereto substantially the same quantity of
chloride in the reaction mixture varying between 3.5 to
4.5:1, cooling the mixture and allowing the mixture to 50 benzene and substantially the same quantity of substan
tially methanol-free aqueous formaldehyde, the molar
separate into upper and lower layers in the reaction ves ratio of water to zinc chloride in the reaction mixture be
sel, removing the upper layer containing benzyl chloride
while allowing the catalyst-containing aqueous lower ing between 3.5 to 4.5:1, reacting the mixture at a tem
layer to remain in the reaction vessel, separating benzyl 55 hydrogen varying
perature
chloride
between 58-63 C., passing gaseous
into said mixture followed by cooling to
chloride from the upper layer, regenerating the catalyst separate the mixture into two layers, removing the upper
in the aqueous lower layer remaining in the reaction
vessel by adding benzene to the reaction vessel followed . layer of said mixture containing benzyl chloride, washing
by substantially completely dehydrating the resultant mix said upper layer with water and an alkali-bicarbonate
ture by azeotropic distillation at atmospheric pressure solution, distilling the resulting solution at about 60 mm.
and at a temperature below 100 C., adding substan 60 pressure, and collecting the portion boiling off between
96-98 C. to obtain substantially the same quantity of
tially the same quantity of benzene, and methanol-free pure benzyl chloride.
aqueous formaldehyde to the regenerated catalyst in the
reaction vessel to form substantially the same quantity References Cited in the file of this patent
of aqueous reaction mixture containing substantially the 65
same quantity of zinc chloride, the molar ratio of water UNITED STATES PATENTS
to zinc chloride varying between about 3.5 to 4.5:1, and 2,541,408 Cockerille ------------ Feb. 13, 1951
then repeating the chloromethylating step to obtain again
substantially the same quantity of benzyl chloride in OTHER REFERENCES
high yield. 70
3. In a process for continuously preparing a quantity Ginsburg et al.: "Industrial and Engineering Chemis
of benzyl chloride in high yield, the steps comprising try," vol. 38, pages 478-85 (1946).