close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3038954

код для вставки
1 _its States
‘is
‘ atent
3,038,944
Patented June 12, 1962
1
2.
3,038,944
. Other aspects, objects and the several advantages of
the invention are apparent from this disclosure and the
S-CHLOROPROPYL, AND 3-CIHJORO-fZ-ME'I‘HYL
appended claims.
According to this invention, 'new chlorinecontaining
sulfoxides have been discovered, these sulfoxides falling
PROPYL ()CTYL SULFIDES AND CORRESPOND
ING SULFOXIDES AND AS NEW COMPOUNDS
3-CHLOROPROPYL-, AND 3-CHLOR0-2-METH
YLPROPYL OCTYL SULFOXIDES
within the scope of one of the formulas
Rector P. Loutlian, Bartlesville, Okla, assignor to Phil
lips Petroleum Company, a corporation of Delaware
No Drawing. Filed Nov. 2, 1959, Ser. No. 850,090
24 Claims. (Cl. 260-607)
10
This invention relates to 3-chloropropyl octyl sulfoxides
and to 3-chloro-2-methylpropyl octyl sulfoxides. In one
of its aspects, the invention relates to at least one of the
and
following compounds:
15
3-chloropropy-l n-octyl sulfoxide
3-chloropropyl sec-octyl sulfoxide
3-chloropropyl tert-octyl sulfoxide
3-chloro-2-methylpropyl n-octyl sulfoxide
3-chloro-2-methylpropyl sec-octyl sultoxide
3-chloro-2-methylpropyl tert-octyl sulfoxide.
20
wherein R is selected from the group consisting of n-octyl,
sec-octyl and tert~octyl radicals.
Also, according to the invention, methods are pro
vided for preparing the sul?des, which are oxidized to
In another of its aspects, the invention relates to a method
the compounds of the invention,‘ and for oxidizing said
of preparing a 3~chloropropyl octyl sul?de which com- sul?des to the corresponding sulfoxides.
prises reacting an octene ~with S-chloropropyl mercaptan. 25 The sulfoxides of this invention are prepared by oxidiz
ing the corresponding chlorine-containing sul?de.
In a further aspect of the invention, it relates to a method
'of preparing a 3-chloro-2-rnethylpropyl octyl sul?de
In preparing the chlorine-containing sul?des from
which comprises reacting an octene with 3-chloroe2
which the sulfoxides are obtained by oxidation, several
methylpropyl mercaptan. In a further aspect of the in—
di?cerent synthesis routes can be utilized. One method
vention, it relates to a method for preparing the last 30 which can be employed is to react ally-l chloride with the
named two types of compounds by effecting the reaction
in the presence of ionizing rays, for example, ultraviolet
light. In a further aspect of the invention, it relates to
desired octyl mercaptan (normal, secondary and tertiary)
in the presence of ultraviolet light. This reaction is car
ried out at a temperature of from ~50 to 200° C., prefer~
the preparation of a 3~chloropropyl ‘octyl sul?de by re
ably from 0 to 100° C. at atmospheric pressure and in
acting an alkali metal mercaptide of an octyl mercaptan
with 1-bromo-3-chloropropane. In a further aspect of
the invention, it relates to preparing a 3-chloro-2-methyl
the presence of ultraviolet light. Ultraviolet light of a
propyl octyl sul?de which comprises reacting an alkali
metal mercaptide of an octyl mercaptan with 1-bromo
2-methyl-3-chloropropane, in one embodiment the reac
wave length of from 100 to 2,900 Angstro-ms is satisfac- '
tory. In forming 3-ch1oropropyl octyl sul?de by this
reaction, the mole ratio of allyl chloride to the octyl
mercaptan is. generally Within the range between 05:1
40 and 2: 1.
It is now preferred to utilize a slight excess of
tion being effected in the presence of methanol under
allyl chloride, i.e., 1.1 to 1.3 moles allyl chloride per
substantially anhydrous conditions. In a further aspect , mole of octyl mercaptan.
still, the invention relates to a method of converting 3
An alternative way of manufacturing the 3-chloro
chloropropyl octyl sul?de to the corresponding sulfoxide
propyl octyl sul?de is to react allyl chloride with hydro
by oxidizing the same with a suitable oxidizing agent as 45 gen sul?de in the presence of ultraviolet light, thus form
ing 3-chloropropyl mercaptan. This compound is then
set forth below. In a further aspect still, the invention
relates to a method of converting 3-chloro-2-methyl
propyl octyl sul?de to a corresponding sulfoxide which
comprises subjecting said sul?de to the action of an
oxidizing agent as set forthbelow.
-_
The compounds of this invention have been found to
be excellent insect repellents and their use in methods
for combatting an insect and compositions containing
them are set forth, described and claimed in copending
_ reacted with an octene in the presence of ultraviolet light
to form the sul?de. In this synthesis route, the ?rst step
is carried out at the same temperatures and ultraviolet
50 wave length as earlier mentioned. ‘Pressures for this re
action will be the autogenous pressure generated by the
charging of the hydrogen sul?de. Mole ratios of hydro
gen sul?de :to allyl chloride will generally be in the range
from 1:1 to 5:1. The pressures generated by the use of
application Serial No. 733,834, ?led May 8, 1958 by Roy 55 these materials in these ratios will generally be from 100
E. Stansburyand Rector P. Louthan.
.
The sulfoxides of the present invention have been
found to be extremely e?icient insect repellents, surpris
ingly, since other sulfoxides which have been tested have
been found wholly unacceptable for repelling insects.
It is an object of this invention to prepare a new com
" pound. It is a further objectlof this invention to prepare
> anew sulfoxide. It is a further object of this invention
to prepare a 3-chloropropyl octyl sul?de. It is a further
objectof this invention to prepare a 3-chloro-2-methyl
propyl sul?de. It is a further object ‘of this invention to
“ prepare a B-chloropropyl octyl sulfoxide. It is a further
object ,of this invention to prepare a 3-chloro-2-methyl
propyl octyl sulfoxide. A further object of the inven
tion is to- provide a method for preparing at least one of
the foregoing compounds.
to 500 pounds. After the S-ch-loropropyl mercaptan is
formed ‘by the reaction of allyl chloride with hydrogen
sul?de, this mercaptan is then reacted with an octene,
octene~1 for example, in the presence of ultraviolet light.
60 Atmospheric pressure issatisfactory for this reaction, and
the vtemperatures and ultraviolet wave lengths previously
"described can be employed. The mole ratio of the 3
chloropropyl mercaptan to the octene usually will be in
the range between 0.5 :1 and 2:1. A 1:1 mole ratio is
65 now preferred.
Onev further alternative method for preparing these
sul?des is ‘to form an alkali metal mercaptide of an octyl
mercaptan and thereafter react this mercaptide 'with 1
brorno-3-chloropropane. For example, tent-octyl mercap
70 tan is reacted with sodium hydroxide to form sodium
octyl mereaptide, and this compound is reacted with 1
3,038,944.
bromo-3—chloropropane to form S-chloropropyl tert-octyl
sul?de.
I
_
Regardless of the method used in forming the sul?de,
the oxidation of this material to the sulfoxide will be the
same.
The now preferred oxidizing agents are peroxygen
compounds selected from the group consisting of hydro
chlorine-containing sulfoxides. The effectiveness of these
alkylene oxides in stabilizing 3-chloropropyl octyl sulf
oxides will be demonstrated ‘hereinafter.
The following speci?c examples illustrate methods for
manufacturing the new chlorine-containing sulfoxides,
their stabilization, and use as repellents. The methyl
group containing compounds of the invention can be
suitable peracids are performic acid, peracetic acid and
readily prepared by one skilled in the art in possession of
perbenzoic acid. These acids can be charged_-to the
this disclosure by using corresponding Z-methyl com
reaction zone as such, or can be generated in situ. A 10 pounds, e.g., 3-chloro Z-methylpropyl mercaptan in lieu
mole ratio of peroxygen compound to sul?de of from
of the 3-chloropropyl mercaptan.
gen peroxide and organic peracids. Some examples of
0.5:1 to 1.5 :1 usually is employed. A now preferred
EXAMPLE I
range is from 0.821 to 1:1. In carrying out this oxida
tion, the sul?de is dissolved in a material which is also
A
run
was
carried
out
in which 3—chloropropyl n-octyl
a solvent for the peroxygen compound. Some examples 15
sul?de
was
prepared
and
subsequently oxidized to the
of suitable solvents are methanol, ethanol, isopropanol
and acetone.
The oxidation usually is carried out at a
corresponding sulfoxide.
In this run, 365 grams (2.5 mole) of n-octyl mercaptan
temperature within the range of from 0 to 100° C., pref
and 200 ‘grams (5 percent molar excess) of allyl chloride
erably from 50 to 80° C. Reaction times are usually
less than one hour, although longer reaction times can 20 were charged to a reactor which consisted of a 9 inch
section of 75 mm. Pyrex glass tubing, closed at one end
be employed. It is preferable to add the oxidizing agent
and provided with a 40/50 standard taper female joint
to the sul?de, always maintaining the sul?de in excess.
fastened in the other end. A glass cooling coil was
This method of operation is preferred to avoid the loss
wound around the inside of the tube to provide a means
of sulfoxide through formation of the sulfone. One con
venient method for determining the end of the reaction 25 for controlling the temperature. Stopcocks were fas~
tened near each end and perpendicular to the axis of
period is to test for peroxygen by means of potassium
the 75 mm. tube so that the reactor could be prevented
iodide-starch paper, a negative test indicating completion
prior to a run and also to provide a means for adding
of the reaction.
additional material during a run. A small stopcock was
An alternative method which is considered suitable for
oxidizing these sul?des is the oxidation of the sul?de 30 also fastened in the end of the reactor containing the
taper joint so that small samples could be removed. A
with oxygen or an oxygen-containing gas such as air.
quartz thimble, 6 inches long, 33 mm. OJ). and pro
This method is best carried out with the addition of a
vided with a flanged joint was placed on the mating joint
small amount of N02 or either N02 or concentrated nitric
of the reactor, and a mercury vapor lamp was fastened
acid plus a bromine-containing compound. U.S. 2,859,
the thimble. The capacity of the reactor was ap
' 248 of R. P. Louthan, issued November 4, 1958 describes 35 in
proximately 700 cc.
and claims a method for the production of an organic
After the reactants were charged, the reactor was
sulfoxide which comprises the oxidation with an ele
mounted on a horizontal shaker ‘and shaken at about
mental oxygen-containing gas of an organic sul?de hav
120 cycles per minute with the mercury vapor lamp on.
ing the formula RSR wherein each R contains not more
than 20 carbon atoms and the total carbon atoms does 40 The contents of the reactor were irradiated at approxi
mately room temperature with the light from a IOU-watt
not exceed 30 carbon atoms and wherein each R is se
mercury vapor lamp until the refractive index at the
lected from the group consisting of an alkyl, cycloalkyl,v
reaction solution failed to increase further. This required
aryl, aralkyl, alkaryl radical, and one of said radicals
approximately one hour. During the irradiation, some
containing a hydroxy group as a substituent, in the pres
ence of a catalyst system comprising a nitrogen compound 45 hydrogen chloride was liberated, and the reaction solution
changed from colorless to a bright orange. The reaction
consisting of at least one of the group consisting of
solution was then transferred to a distillation flask, and
HNO3 and N02 and a halogen compound consisting of
at least one of the group consisting of CuCl;, CuBr, , most of the unreacted allyl chloride was stripped oif at
atmospheric pressure by heating to 150° C. The remain
CuBr2 and HBr, with the proviso that, where one of the
R’s contains a hydroxy group, HBr is not selected.
mg material was distilled at reduced pressure to yield 302
50 grams of 3-chloropropyl n-octyl sul?de, B.P. 145° C. atv
Furthermore, in preparing the sul?des by one of the
7.0 mm. Hg absolute, nD2° 1.4770. This corresponds to,
above-described routes, it is bene?cial to utilize a small
a 62.7 percent conversion of the mercaptan. One hun
amount of a hydrogen chloride scavenging agent such
dred and thirty six grams of unreacted n-octyl mercaptan
as ethylene oxide or propylene oxide. Copending appli
cation, Serial Number 802,031 of R. P. Louthan, ?led 55 and 41 grams of high boiling material were also re
covered. Thus, the ultimate yield of 3-chloropropyl
March 26, 1959, describes and claims a method of pro
nz-lgityl
sul?de was 86.3 mol percent
based on the mer~
moting a reaction between a sulfur-containing compound
c
an.
‘
which is reactive with a halogen-containing ole?nic com
In a similar run, the same charge was irradiated with
pound in the presence of activating rays to produce a
compound selected from the group consisting of a thiol 60 the light from a 450-watt mercury vapor lamp in place’
of the 100-watt lamp. Again, ‘irradiation while shaking
and a sul?de which comprises eifecting the reaction in
was _carr1ed out until a constant refractive index was
the presence of a material selected from the group con~
obtained. In‘this run, a reaction time of less than 15
sisting of an anion exchange resin and an epoxy~contain~
ing organic compound.
minutes was required.‘
,
The oxidation of this sul?de to the cor-responding sulf~
According to the present invention, these alkylene ox 65
oxide, 3-chloro-propyl n-octyl sulfoxide was carried out
ides can be present in the reaction mixture wherein the
in a 3-necked ?ask, ?tted with a stirrer, a re?ux condenser
sul?des are oxidized to the sulfoxide. Furthermore, a
and a dropping funnel‘. In a typical run, 222.5 grams oi
small amount of these alkylene oxides in the new chlorine
3-chloropropy-l n-octyl sul?de and 300 cc. of‘ methanol
containing sulfoxides of this invention are bene?cial in
preventing dehydrohalogenation during storage. These 70 were charged to the ?ask and heated to re?ux. At this
time, 113.3 grams of 30 percent by weight aqueous hy
compounds apparently inhibit the decomposition via de
drogen peroxide was then‘ added over a 20 minute period.
hydrohalogenation, or they scavenge the hydrogen chlo
ride which is generated. In any event, the use of these
The reaction mixture re?uxed vigorously during the H202
addition. After all' of the hydrogen peroxide had been
alkylene oxides, helps to prevent corrosion caused by
added, the solution was allowed to stand at least two
generated hydrogen chloride during storage of these new 75 hours
to complete the oxidation. Then, about 500 cc. of
3,038,944
5
water was added to precipitate this product as a second
liquid phase.
6
Table III
’
Alternate methods were used to I‘CCOVBI‘ the product.
Run No ______________ __
O
D
E
F
G
750 cc
750 C0
750 cc,
1_5g5],1_
100
100
100
450
The ?rst method consisted of extracting the product with
a solutlon of 500 (33- of n'pentane together With 250 CC.
of ether.
5 Reactor size _________ __ 750 w
The‘ product was then crystallized from the
Ultraviolet Lamp size,
pentane-ether solution at ‘dry ice temperature. In an-
100
0113;?
other run, the product from the H202 oxidation of 3-
3-°h1°r°Pr°PY1
277
277
277
277
11197
chloropropyl n~octyl sul?de was extracted with 250 cc.
oéti?iit’igltigtu 280
280
280
280
1,215
of chloroform, after which the chloroform was stripped 10
Additive ......... -_ None
None
01f by heating to 80° C- at 2 mm. of Hg absolute pressure,
A‘?‘j‘i?t’g
fihvsitr‘leri‘lglgerit the crystallization method are shown beT bi
a
I
e
(1')
(1’)
"""""""" " 0'1 g‘
10 cc‘
None
"""" '“
lllfiégglif?gfgn??ami 50
50
£1“)
{1,0
ho
Product Recovered
394
402
401
420
1,612
70.0
72.2
72.0
76.3
66.8
100
100
100
100
100
Grams)“
15 Conversion of Reoetents (percent .
Physical Pl'opoy?os of
Mgl ilgep
cen 0
Recovery Method
Sulfoxide
Ultimate yield por-
‘
cont)
ulf
0511333313321 Approx Refractive
aglphaialpha?zodlisobutyronitrile.
Plblifrlttgntgl, Indexnnm 2'0 oa-gglliiigrlilfogélgloctyl sul?de.
._
.
uysmmmion """"""""" “
83‘4
3H0
_
1' 4740
A portion of the 3-chloropropyl n-octyl sul?de, prepared
by the method described above was then oxidized to 3
chloropropyl n-octyl sulfoxide by means of hydrogen
25 peroxide. The apparatus employed was identical to that
EXAMPLE II
Several runs were carried out in which 3-chloropropyl
used in the oxidation step of Example _I. In this run, an
amolmt of hydmger.‘ Peroxide less thing that theoretically
n-octyl sul?de was prepared by another syn-thesis route.
reqmred for the oxldatlon was employed‘ Accordlngly’
In these runs, allyl chloride and an alkylene oxide were
2225 grams of 3'chloropropyl n'octyl sul?‘ie’ 300 cc‘ of
charged to a 1.5 gallon stainless steel reactor which was 30 methanol’ and 102 grams of 30 PerFent, by Welght hydrogen
equipped with a‘ means for irradiating the contents with
ultraviolet light. After the allyl chloride was charged,
peroxide were, chargefljto the ({Xtda?on reactor’ tile hy'
drogen pewxlde 'addltlqn requmng 211191" 10 mlmftes'
' hydrogen sul?de was charged to the reactor, and the con-
After 16 mmutes’ 3' neganve test for p‘iroxlde was obiamed
tents'were irradiated with a 450-watt mercury vapor
Wlth Kl‘starch paper’ so the reactlon was consldered
lamp.
After irradiation, the unreacted hydrogen sul?de .35 complete-
was vented, and the remaining reaction solution was distilled. Most of- the unreacted allyl chloride was ‘stripped '
off ‘by heating the solution to 150° - C_ at atmospheric
1 _ pressure. The product, 3-.chloropropyl mercaptan (B.P.
_
_
,
-_
The reactlon Solution was ‘muted Wlth 500 cc- of Wat?"
and the Product Phase was Wlthdrawn and extmqted Wlth
500 cc. of n-pentane. The pentane was then stripped off
'
under reduce‘? Pressure-
The Product’ 3'chlompropl"1
68°C. @ 50 mm. Hg absolute and B.P. 145° C. @ 769 40 n-octyl sulfoxlde, amounted to 232.1 grams.
mm. Hg‘absolute, nD2° 1.4935) was distilled from the
strippedl'reaction solution at 50 mm. Hg absolute. The -
.
date for" the two runs were summarized in the following
table.
'
I
Table H r
Ch
We’
?gii?gé?riiiéiagfiaiéi """"" "
?i§¥égléeog§ége(c(gci)—M01
-
5' léial-lyl-b-
,lltgigggtg’giulgieg minutes- "" "
‘Product: seilioml‘siapir'i'iiiéiééiiéif25511;;III
Byéfgglslft" 3'3"‘mh mudipmpyl sul?de
Iconversioii'oiliiiyf?hloiidefnereenti
.
, EXAMPLE .111
A run was earned out "1 Whlch 3-Ch1OYOPYQPYI 566
octyl sul?de was preparedand subsequently oxidized to
3-chloro ropyl sec-octyl sulfoxide.
45
In this run, 138.6 grams of sec-octyl mercaptan, 80
grams ofv allyl chloride and trace of thio-(3-naphthol)
R1134
R1111 B
were charged to the reactor of Example I and irradiated
with. ultraviolet light. The thio-(S-naphthol) was ern-'
ployed for the- purpose of promoting the reaction, but
iigiig
k311i.) 50 no promoting eifect was obtained. After 70 minutes,
100 ------- “£66
the light was turned oil, and the reactor contents were
""""
2
3g
1,190
346
58
removed.
Distillation of the reactor contents resulted in
132
the isolation of 94.6 grams of 3-chlorpropyl sec-octyl sul
1,180 55 '?de, B-P- 132° C- @ 55 mm- Hg absolute The refrac
423
tive index of ‘this material was nD2°=1.4765.
61
This sul?de was then oxidized to the sulfoxide as de
scribed in Example I, utilizing a charge of 75 grams of
3-chloropropyl sec-octyl sul?de, 115 cc. of methanol and
Several runs were then carried out in which the 3-chloro- 60 36 grams of 30 percent by Welght aqueous H202‘ 6.9'8
' propyl mercaptan, prepared as described above, was regrazgns of crude g'qhloroprop Y1 secioctyl suifoxlde’
acted with octene-ldn the presence of ultraviolet light.
"D =1'4820 was obtamfedh The sulfoxlde 1s pun?ed by
In these runs, the reactants were charged to a reactor,
low temperature crystalhzatmn to produce the Pure com‘
after which the reactor was purged with nitrogen. The
pound‘
‘reaction mixture was then irradiated for the desired time 65
period, after which the reaction solution was distilled at
reduced pressure. Most of the unreacted ootene-l and
EXAMPLE IV
In another run, 3-ch'loropropyl tert-octyl sul?de was
prepared and subsequently oxidized to ,S-chloropropyl
3-chloropropyl mercaptan was taken overhead as one cut
tert-octyl sulfoxide.
.
(50 to 74° C. @ 75 mm. Hg absolute) by heating the
In this run. 197 grams of tert-octyl merca-ptan, 25
pot to 150° C. @ 75 mm. Hg absolute. The pressure was- 70 cc. of methanol, and 59' grams of NaOH were charged
then reduced to 12 mm. Hg absolute, and after taking 3
to a 1-liter, 3-necked ?ask equipped with a stirrer and
small intermediate cu-ts (1212 39-158“ 0.), the remaining
3-chloropropyl n~octyl sul?de was ?ashed overhead at
158-160° C. @ 12 mm. Hg absolute pressure. Theruns
are summarized below in the form of atable.
75
heated at re?ux until all of the caustic had gone into solu
tion. This solution was then tnansferred to a dropping
funnel and 212 grams of l-bromo-S-chloropropane was
charged to the flask. The sodium mercaptide was then
3,038,944
7
8
added .dropwise over about a ZO'rninute period. The re-'
action was quite vigorous and sodium bromide precip
itated out. After stirring a few minutes to complete the
pounds.
EXAMPLE VII
reaction, about 250 cc. of water was ‘added to dissolve
,
the salt (NaBr). The phases were then separated, and
the oil phase was washed with dilute HCl and then with
Water.
This phase was then, distilled. The major cut,
amounting to 282.0 grams, had a refractive index of
"D20: 1.4855 and boiled at 117° C. @ 5 mm. Hg ab
solute.
I
I
I
The 3-chloropropyl tert-octyl sul?de, prepared as de-'
OLF'ACTOMETER TEST
The olfactometer'is an instrument that supplies two '
streams of air to a cage. Onestream passes through a
?lter on [which some of the candidaterepel-lent has been
placed. The other'stream. is not treated and serves as a I
10 control. To conduct an olfactometer test a 0.1 gram
' sample of the repellent is dissolved in acetone and the
solution is used to saturate a ?lter pad (American Optical
scribed above, was then oxidized to the sulfoxide as in
Example I.’ The chargefor this oxidation was 100 grams
of S-chloropropyl tert-octyl sul?de 150 cc. of methanol
,and 48 grams of 30 percent by weight aqueous H202.
The material was Worked up by stripping (see'ExampIe a‘
I), and’ 87.3 grams of 3-chloropropyltert-octyl sulfoxide '
(11132°=1.4993) was recovered.
EXAMPLE V
Several runs were carried out inwhich 3-chloropropyl ' 29
n~octyl sulfoxide, prepared by the method described above
ing certain amounts ofpropylene oxide were heated in an
oil bath at 115 to 120° C., and the time required for de
composition was measured. .At this temperature, the de
composition point was very marked, as the material be
gan to turn yellow with the evolution of gas, and the 30
of these runs are expressed below in the form of a table.
'
Sample No.
Table IV
Additive
'
Amount of Time to De
Additive
eomp'ost- '
(weight
percent)
tlon,
minutes
0
0. 5
1. 0
5.0
10.0
11
29. 5
55. 0
>180
>180
Company R-7 ?lter pad of the type used in respirators).
The pad isair dried, and ?xed over ametal tube. A glass
cylinder is then ?xed over the pad. This cylinder (about
4" ID and 6" long), in turn, is placed in contact with
the wire surface of the insect cage.
Similarly, an un
treated pad is set up as acontrol.
Air is blown at the same volume rate through both
pads.
The number of house ?ies on the screen wire with- ' I '
in‘ the area-outlined ‘by the glass cylinder is counted after
5, l0 and 15 minutes and at 15 minute intervals there- "
after until ten readings have been made. The average I
of thesev tenreadings is used to determine the percent in
in Example I, was admixed with various amounts of addi
tives and heated to determine its stability.
In these runs, small amounts of the sulfoxide contain
color rapidly changed from yellow to black. When do
composition began, only 15 to 30 seconds were required
for the material to go through this change. ‘They results
.
according to the invention, as compared with other com
crease or decrease in number of ?ies on the treated
circles.
The results .of-olfactometer tests showed that no ?ies
alighted on the wire when the air was ‘?ltered through a
pad treated with 3-chloropropyl n-octyl sufoxide.
The
control test gave an average of 16.2 ?ies. ' The sulfoxide
was completely effective in repelling ?ies by this test.
EXAMPLE VIII
SANDWICHVBAI'I‘ TEST
7 This test involves placement of a porous barrier treated
withythe candidate insecticide between the starved in—'
sects (house ?ies) and food. If 'the'che‘mical'is re
pellent, the. ?ies will not eat. If the chemical is not
repel-lent, the insects will eat the food through the barrier.
40
The bait is prepared as follows: A smooth thin'?lm
of unsulliured molasses ispspread on a -1" x 4" strip of
. cardboard leaving a margin of at least 1A inch on all
sides. The purpose of the margin is to prevent the feed
ing of the insects unless they are actually on the strip,
thus facilitating counting. These prepared strips are dried
It can be seen from the above runs that an alkylene
in the oven at 45° C.
Porous cover strips of lens paper are impregnated
with the chemical under examination and superimposed
on the bait. The paper is thin, porous, and highly absor
vention.
50 bent. The loose ?ber construction of this paper per
EXAMPLE VI
mits the ?y to remove the molasses through it. In order
A run was also carried out in which 3-chloro-2-methyl
to impregnate these strips uniformly, they are immersed
propyl n-octyl sul?de was prepared and subsequently
in an acetone solution of the material to be tested. They
oxide, e.g., propylene oxide, is very effective in prevent
ing the decomposition of the new sulfoxides of this in
oxidized to 3-chloro-2-methylpropyl n-octyl sulfoxide.
In this run, 100 grams of methallyl chloride and 146
grams of n-octyl mercaptan were reacted in the presence
are then hung over a glass rod and dried for 6 hours.
Just before the test is begun, the dried cover strips
are carefully placed over the baits and fastened in place
of ultraviolet light by essentially the same procedure de
scribed in Example I. An extraction-stripping recovery
procedure, essentially the same as described in Example
press down on the bait or touch it with the ?ngers as
I, yielded 3-chloro-2-rnethylpropyl n-octyl sul?de, B.P.
Two sandwich baits are attached to a cardboard back
147° C. @ 5 mm. Hg absolute pressure. The refractive
index of this compound was nD2°=l.4751.
The sul?de was then oxidized to the sulfoxide by the
oxidation procedure of Example I, using 75 grams of
3-chloro-2-methy1propyl n-octyl sul?de, 100 cc. meth
anol and 36 grams of 30 percent by weight aqueous hy~
drogen peroxide. The reaction mixture, after comple
by stapling. In assembling the bait, care is taken not to
the molasses is easily forced up through the cover strip.
ing. The whole assembly then is taped onto one of
the jar lids that ?t the opening in the rubber back of the
insect cages.
The lid with the baits is ?tted into an aperture in a
cage so that the baits are exposed to attack. Flies over
?ve days old which have been starved for six hours are
used. Counts of the number of ?ies ‘feeding on the
tion of the reaction, was extracted with pentane, and the
strips ‘are taken after ?ve and ?fteen minutes and every
sulfoxide was recovered by stripping oil the pentane at
fifteen minutes thereafter for two and a half hours. In
62° C. @ 1 mm. Hg absolute pressure. The 3-chloro-2 70 some cases where the chemical is not repellent, the flies
methylpropyl n~octyl sulfoxide obtained amounted to
eat all the molasses before the two and one half hours
79.9 grams, and the refractive index of 'this compound
are up. In this case, counts are discontinued. The non~
was nD2°==1.4826.
repellents become black with ?ies soon after being placed
The following example illustrates the unexpected ex
in the cages. The good repellents are untouched. The
cellent repellent properties of the compounds prepared 75 dliference
is very striking.
a
3,038,944
9
a.
.
.
Table V summarizes the results of sandwich bait tests.
10
2.
Tests 1, 2, 3 and 4 wherein 1 percent acetone solutions
were used as well as tests 5 and 6 wherein 0.5 percent
H H H 0
C1__é_é__‘|3_| 410cm
solutions were applied show the effectiveness of the com-
£1 gl Ill
pounds having as one substituent the 3-chloropropyl or 5
the 2-methyl-3-ch-loropropyl group and as the second
.
3'
substituent a normal, secondary or tertiary octyl group.
Related compounds, such as those applied in tests 7 to
1
1|1 H H (1’
o1—o—rl‘—<lJ- ~seooctyl.
18 were ineffective at comparable dosages.
A; Ely
Table V.—-Sandwich Bait Test With House Flies Using
’ Various Sulfoxides
Number of ?ies feeding at indicated time (minutes)
_
Sulfoxide
’
'
5
15
30
45
Bait 195%
After
Overnight
Percent a
60
75
90
105
120
135
150
165
’
Exposure
Siizlifoxides
used as 1% Acetone Solu
ODS!
3-chloropropy1n-octy1 ........... _.
3-chl0r0‘rir0pyl sec-octyl ......... ._
2-methy -3-chloropropy1n-octyl...
0
0
0
0
0
0
0
1
o_
0
o
0
0
0
3-chloropropyl tart-octyl ......... ..
0
0
0
0
0
‘ 0
0
0
0
0
o
0
0
1
0
0
1
1
1
,
0
0
1
0
0
0
0
0
0
1
0
0
0
0
0
1
4
0
100
0 __________ ..
B 94
0
0
0
4
l
4
n 98
0
0
0
0
0
0
100
0
0
0
1
1
4 .......... .
siilfoxides
used as 0.5% Acetone Solu
lOIlSI
3-chloropropyl n-octyl ......... ._
2-methy -3-chloropropyl n-octy .._
Srzliorcides used as 1% Acetone Solu101152
Y
3-chloropropyln-amy1 ........... __
3~hydroxypro yl n-octyL.
3-chloropropy n-butyl-._
3-chloropropyl tert-butyl.
3-chloropropylisobuty1_.__-
'
4
12
32
50
42
50
50
28
28
25
22
12
(b)
12
(b)
50
19
2
10
3-chloropropyl 2-ethylhexyl ______ __
0
12
15
3
0
15
0
22
0
0
0
' 0
3-ch1oropropyl 2,4,4-trimethyl-1-
penty .'
_
B-chloropropyl tert-dodeeyl ...... -_
3-chlo1ropropy1 dlcyclopentadienAlkyl Sult'oxides used as 1% Acetone
.
0
_
_
.
__.
6
.
s
5
14
eny .
Part D:
‘
Solutions:
di-n-butyl ....................... l-
n-octyln-prop
.
tort-octyl methyl ................ ._
0
0
'4
20
3
3
3
3
15
28
30
25
(h)
_ ___ _ _
0
0
(b)
0
. . _ _ __
____ __
1
____ __
1
______
6
.__...
.......... .
. _ _ _ . . . _ _ . ._
e Observation after starving ?ies 165 minutes.
b Food is gone at the indicated time and hence the test is terminated.
1 " After exposure overnight to starving ?ies.
Reasonable variation and modi?cation are possible
4,
within the scope of the foregoing disclosure and the ap
pended claims to the invention the essence of which is
ill 1'1 I? (I)
that there have been provided new chlorine-containing 45
sulfoxides which are B-chloropropyl octyl sul-foxides and
-
Q1_<3_0__c_h.termdty1.
III A I
3-chloro-2-methylpropyl octyl sulfoxides; methods for
.
-
preparing sul?des which can be used in the preparation
5.
_ of the sulfoxides, the methods essentially comprising re~
acting an ootene with a S-chloropropyl- and/or 3-chloro~ 50
H CH3 H 0
Z-methylpropyl mercaptan, and reacting ‘an alkali metal
mercapude of an octyl mercaptan with 1-bromo-3-chloro~
.-
.
_
01 A;
| 1
__
propane and/or -1-bromo—3~chloro-2-methylpropane; a
method of converting a sul?de to corresponding sulfoxide, speci?cally the sulfoxides of this invention, which
comprises oxidizing the sul?de corresponding to the sul-
r
0
1% mm 1
_
ll:
_
y
6
'
H CH3 H O
01 (I3
_111-&
60
I claim:
1. A compound having one of the formulas
'
“
LL g
t l
f ‘Wm y‘
H
7
H“
were
01-E:_(|3_?_g_
H H
_
_
H H
foxide of this invention to a su-lifoxide under conditions
to yield said sulfoxide; and a stabilized sul-foxide product
comprising an alkylene oxide stabilizer therein.
H
65
O1——C——(|3~———~(|3—
-tertoctyl
h H 11
I
and
8. A method of preparing -a S-chloropropyl octyl sul
?de which comprises reacting an octen'e with 3-chloro
70 propyl mercaptan.
1% k
I
1;!
9. A method of preparing a 3-chloro-2-methylpropyl
'
octyl sul?de which comprises reacting an octene with
11
3-ehloro Z-methylpropyl mercaptan.
wherein R is selected from the group of n-octyl, sec10. Amethod according to claim 8 wherein the reaction
. octyl, and tert-octyl radicals.
75 is effected in the presence of ultraviolet light irradiation.
3,038,944 '
12
11
11. A method according to claim 9 wherein the reaction
is effected in the presence of ultraviolet light irradiation.
12. A method of preparing a 3-ohloropropyl octyl sul
?de which comprises reacting an alkali metal mercaptide
of an octyl mercaptan with 1~bromo-3-chloropropane. .
IV
13. A method of preparing a 3-chloro-2-rnethylpropyl
octyl sul?de which comprises reacting an alkali metal mer
captide of ‘an octyl mercaptan with labromo-2-methyl-d
wherein octyl is selected from the group 11, sec, and tert
octyl radicals, which comprises subjecting said sul?de
chloropropane.
to the action of a peroxygen compound in the presence
14. The method of claim 12 wherein the reaction is 10 of a solvent which dissolves both the sul?de and said
peroxygen compound.
effected in the presence of methanol under substantially
anhydrous conditions.
20. A method of converting a compound selected from
15. The method of claim 13 wherin the reaction is ef
fected in the presence of methanol under substantially
anhydrous conditions.
16. A method of preparing a 3~chloropropyl octyl sul
?de which comprises reacting an octyl mercaptan dissolved
9 compounds having the formulas identi?ed as III and IV
in claim 19 which comprises oxidizing said compound
15 with oxygen in the presence of ‘an oxygenated compound
of nitrogen which acts to convey the oxygen to said com
pound.
21. A method of converting a compound selected from
compounds having the formulas identi?ed as III and IV
in claim 19 to the corresponding sulfoxide which com~
in methanol with an alkali metal hydroxide, adding the
reaction product thus obtained to labromo-3'chloropro
pane, obtaining sodium bromide precipitate, separating an
oil phase by adding water to obtain ‘two phases and remov
ing the water phase which now contains sodium bromide
and obtaining said sul?de from the oil phase.
prises oxidizing said compound with an oxidizing agent
under conditions to yield said sulfoxide.
22. A stabilized compound selected from compounds
the formulas identi?ed vas I and II in claim 1,
17. A method of preparing 3-chloropropyl octyl sul 25 having
the stabilizer being an alkylene oxide.
?de which comprises reacting an octene-l ‘and S-chloro
23. A method of preparing 3-chloropropyl n~octyl sul~
propyl mercaptan in the presence of ultraviolet light hav
?de which comprises reacting n-octene~1 with 3-chloro' ‘‘
ing a wave length in the range IOU-2,900 Angstroms.
propyl mercaptan.
‘
18. A method of preparing 3—chloro-2~methylpropyl
24. A method of preparing 3-chloro-2-methylprepyl
octyl sul?ed which comprises reacting an octene-l and 30 n-octyl sul?de which comprises reacting ndocteneal with
3-chloro Z-methylpropyl mercapt-an in the presence of
3~chloro~2~methylpropyl mercaptan.
‘
ultraviolet light having a Wave length in the range 100
References Cited in the ?le of this patent ‘
2,900 Angst-toms.
19. A method of converting a sul?de having one of
35
the formulas
H H. H
UNITED STATES PATENTS
2,392,294
Rust et a1. ________ -_-____ Jan. 1, 1946'
2,392,295
Rust et a1. ____________ __ Jan. 1, 1946
2,802,035
Fincke ________ _‘........_-.... Aug. 6, 1957
OTHER REFERENCES
III
40
Buckley et aL: J. Chem. Soc. 1947, 1515.
Документ
Категория
Без категории
Просмотров
2
Размер файла
1 019 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа