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2,411,869
Patented Dec. 3,. 1946
UNITED. STATES _ PATENT, orrica
ADDITION REARRANGEMENT PRODUCTS OF
THIOCYANIC ACID‘ AND CYCLOPENTA
DIENE-OLEFINIC ADDUCTS
Herman A. Bruson, Philadelphia, Pa.~, assignor to
'
The Resinous Products & Chemical Company,
Philadelphia, Pa., a corporation of Delaware I
No Drawing. Application October 6, 1944,
1
Serial No. 557,554
6 Claims.
(Cl. 260-454)
This invention relates to addition-rearrange‘
ment productsof thiocyanic acid and cyclopen
tadiene-mono-ole?nic adducts.
'
Thi'ocyanation of organic compounds has here
tofore been accomplished by replacement of a
halogen atom or a sulfate or phosphate ester
group by reaction with a salt of thiocyanic'acid,
or by addition of 'thiocyanogen to both sides of
a multi-bonded linkage of carbon atoms, or by
2
such as calcium thiocyanate, or ammonium thio
climate.- One or more of such salts may be used
over a wide range of concentration- Dilute so
lutions up to super-saturated solutions may be
employed.
To liberate thiocyanic acid from these salts‘,
there may be used non-oxidizing mineral acids
over a considerable range of concentration. Ac
ids such as hydrochloric, sulfuric, and phosphoric
are particularly suitable and may advantageously
be used at concentrations‘ from 10% to about 40%
although weaker and more concentrated solutions
addition of thiocyanic acid to certain unsaturated
hydrocarbons having reactive double bonds;
whereln‘there are used inert, anhydrous organic
are also useful. The acid and thiocyanic acid
solvents at relatively low temperatures and where
salt
are desirably used in equivalent proportions.
no rearrangement of the hydrocarbon occurs. It‘
Incarryingout
the reaction, the salt and acid
15
has beenv gen'erally'held impractical to work with
are graduallycombined or mixed in the presence
thiocyanic acid because it readily polymerizes at
room temperature or in aqueousv solutions to a
of water and in the presence of the cyclopen- '
tadiene~mono—ole?nic adduct employed.
The ‘.
yellow insoluble compound. For this reason it
latter may be stirred with an aqueous solution of
can be handled only in dilute, inert, anhydrous
solutions; for example; ether, at ice bath tem 20 the salt, and the acid added thereto little by lit-"
tle-.. On- the'other hand, the salt or- a solution
peratures, and gives very poor yields of product.
or a suspension thereof may be added gradually
In accordance with the present invention, how
to .a stirred mixture of the acid and the cyclo-.
ever, it has been found that by operating under
pentadiene-mono-ole?nic adduct. The latter
conditions contrary to the prior art; namely, in
may also be added directly‘ to a solution of the
‘the presence of water and atv elevated tempera 25 ‘mineral-acid
or of the thiocyanate salt in water
tures, cyclopentadiene-mono-ole?nic adducts can
or in a mixture of water and an organic solvent,
be reacted smoothly with thiocyanic acid to form
good yields of new hydrothiocyanates and iso
thiocyanates in which a rearrangement of the
initial ring system has occurred. By operating 30
at temperatures from about 30° C. to 100° C. and
in the presence of water, the rate _of addition of
the thiocyanic acid to the double vbond is appar
ently greater than the rate of polymerization of
the . thiocyanic acid itself. ‘* Furthermore, the, 35
products obtained as a result of the reaction area
not simple addition products per se formed by the
addition of thiocyanic acid to. the double bond,
particularly one miscible with water such as ace
tone or ethyl alcohol.‘ Or the cyclopentadiene
mono-ole?nic adduct can be dissolved in a water- ,
immiscible solvent such as benzene, the ?nely
powdered thiocyanate salt added thereto, and
the mixture rapidly stirred while an aqueous so
lution of the mineral acid is gradually added
thereto. This is particularly useful if the ole
?nic compound is a solid or is highly viscous.
According to this invention, there is thus lib
erated at- any given moment only a relatively
small amount of thiocyanic acid in a reaction
but are molecular ‘ rearrangement products
medium
containing water and the cyclopentadi
40
formed by a rearrangement of the ring. It is
ene-mono-olefinic adduct with or without the
remarkable that even at 90° C.’-l00° C. and in
presence of an'organic solvent, at a temperature
the presence of water only traces ofrpolythiocy-i
su?‘lciently high for the desired addition and
anic acid are encountered and that even in those‘
rearrangement to occur as rapidly as the ‘thio
cases where extreme susceptibility to cleavage
would be expected, as, for example, in the case 45 cyanic acid is‘ formed, thereby practically elim
inating the polymerization of the latter. For
of esters, good yields of the rearranged hydro
this
purpose a reaction temperature between
thiocyanates and isothiocyanates are obtained.
about 45° C. and 100° C. has been found most
In effecting the reaction between the cyclopen
advantageous.
'
'
tadiene-mono-ole?nic adducts and thiocyanic ac
The process disclosed herein is applicable to a
id, there can be used as the source of the thio 50
wide variety of cyclopentadiene-mono-ole?nic
cyanate group an aqueous solution or suspension
of a salt. of thiocyanic acid. ‘By 'way of exam-'
ple‘,‘there may be cited as suitable salts alkali
thiocyanates including lithium, sodium, or potas
sium 'thiocyanates, alkaline earth thlocyanates,
adducts of the Diels-‘Alder type.
For exampl ,
the process is applicable to the Dials-Alder type
adducts of cyclopentadiene and the following
mono-ole?nic ‘compounds; thatis, compounds
'
2,411,869
4
3
maintained at 90°-95° C. during the addition of
having an open-chained group containing a dou
ble bonded linkage between carbon atoms:
the hydrochloric acid and for twenty-?ve minutes '
thereafter. The product was washed with water, _
Ethylene, propylene, styrene, pl-bromostyrene,
ally] alcohol, allyl chloride, vinyl chloride, vinyl
filtered, and dried. The clear oil obtained was
then distilled in vacuo.
The product boiling at 155°-160° C./7 mm. was
acetate; allyl esters such as allyl acetate, allyl
oleate, allyl benzoate, allyl salicylate; allyl ethers,
for ‘example ally] phenyl ether, allyl naphthyl
ether, allyl chlorophenyl ether, allyl cyclohexyl
ether, allyl benzyl ether, allyl benzyl sul?de, allyl
a colorless oil, corresponding in composition with
compounds of the probable formula
CH
butyl sul?de; 1,2-dichloroethylene, allyl benzene, , 10
Cg]: -\CH|
l H' l
eugenol, safrol, croto'naldehyde, acrolein, methyl
vinyl ketone, and other zip-unsaturated alde- _
hydes-or ketones.
.
lg
_
H,- -——
The products are useful as toxicants for the
preparation of insecticides. They also possess 15
parasiticidal activity.
;
In order to illustrate this invention more fully,
the following examples are given. ;
Example 3
-
To a rapidly stirred mixture of 50 g. of water,
Example 1
To a rapidly stirred mixture consisting of '46 g.
20 48.5 g. of sodium thiocyanate, and 92 g. of 2,5
endom'ethylene - A 3- tetrahydro - benzylphenyl
of ammonium thiocyanate, 48 g. of'water, and
ether
62 g. of 2,5-endomethylene-A3-tetrahydro-benzyl
alcohol
(oNs)
on
,
25
Lite
Ha
80 (wherein R is a phenyl nucleus, as a speci?c ex
ample of aromatic hydrocarbon nuclei including
(cyclopentadiene-allyl alcohol adduct)
naphthyl, substituted phenyl, “ and substituted
naphthyl groups) maintained‘ at 95°-99° 0., there
there was gradually added dropwise 60 g. of con
centrated 35% hydrochloric acid during the
was gradually added 60 g. of concentrated hydro
course of twenty minutes while the reaction tem 35 chloric acid during the course of twenty minutes.
perature was maintained at 40° C.-45° C. by
The mixture was then heated further at 95° C. for
means of a warm water bath. After all the hy
twenty minutes, then washed, ?ltered, dried, and
drochloric acid had been added, the mixture
distilled in vacuo.
was stirred for one hour longer at 40°-45° C. and
'
The product boiling at 180°-182° C./0.5 mm.
allowed to stratify. The oil layer was separated 40 amounted to 91 g. It was a colorless oil having
the properties of an isothiocyanate of the proba
ble formula
by means of a little benzene and the benzene
. solution washed thoroughly with water, ?ltered
from traces of polythiocyanic acid, dried, and dis
tilled in vacuo.
The product boiling at 169°-172° C./6 mm. was 45
a colorless oil having the properties of a saturated
thiocyanate and of the corresponding isothio
cyanate, indicating that the product is a mixture
of thiocyanate and isothiocyanate, of the proba
ble formula
when heated with concentrated ammonium hy
droxide solution, it yields the corresponding thio
urea as a crystalline compound, melting at 135° C.
The 2,5-endomethylene-na-tetrahydro-benzyl
55 phenyl ether used is a colorless oil boiling at
133°-136° C./6 mm. obtainable by boiling dicyclo
pentadiene with allyl phenyl ether.
((lJNS)
Example 2
Example 4
I
60
chloric acid was added dropwise during the course
To a rapidly stirred mixture of 35 g. of water,
32.4 g. of sodium thiocyanate and 70.4 g. oi’ 2,5
of ten minutes to a rapidly stirred mixture of 20
g. of water, 20 g. of ammonium thiocyanate, and
phenyl ether
Twenty-?ve grams of concentrated hydro
38 g.
endomethylene - A3 - tetrahydrobenzyl-o-chloro
of 2,5 - endomethyl-M-tetrahydrobenzyl 65
acetate
0
or
H m
on
\
70
CH-O-C o-cm
which is obtained‘ by reacting cyclopentadiene
with vinyl acetate, The reaction mixture was
maintained at 95° 0., there was added dropwise
40 g. of concentrated hydrochloric acid during
the course of ten minutes. The mixture was then
stirred for one hour longer at 95° C. It was
2,411,869
6
.
-
was then stirred ten minutes longer at 95° (2.,
cooled, mixed with 500 cc. of waterand the oil
taken up in benzene. The benzene layer was
The benzene was distilled off in vacuo and the
residual oil (84 g.) distilled in’vacuo. The prod
uct (68 g.) boiling at 201°-204° C./1 mm. was a
?ltered, washed, dried, and distilled in vacuo.
thick, pale yellow oil having the properties of an
The product boiling at 215° C./1 mm. was a
isothiocyanate of the probable formula
viscous, pale yellow oil having the properties of
an isothiocyanate of the probable formula
C
‘
l ml ~63
'
on
c€l\cn,
H] l
l
15
The 2,5-endomethylene-A3-tetrahydro-benzyl
..
m-l- -cm-o-co-©
N=C=S
o-chlorophenyl ether used is a colorless oil boil-_
ing at 130°-.134° c./1 mm. obtainable by boil
_
The yield of .product amounted to 100 grams.
ing dlcyclopentadiene with allyl-o-chlorophenyl
Example _7_
20v
ether.
.
wise 70 g. of concentrated hydrochloric acid dur
ing the course of twenty minutes. The mixture
cooled, taken up inbenzene, ?ltered, and the
benzene solution washed thoroughly with water.
Example 5
'
A mixture of 324 g. of safrol (2 mols) and 139 .
g. of dicyclopentadiene (1 mol) was heated under
A mixture of 104 g. of dicyclopentadiene and
183 g. of allyl-p-(a,amr-tetramethyl-butyl)
a re?ux condenser at 160°-170° C. for fifteen '
phenyl ether was boiled under a re?ux condenser
hours and the product then distilled in vacuo.
at 160°-175° C. for eight hours, and the product
then distilled in vacuo. The compound having
the formula
25" The desired product having the formula
C
‘
CH
distilled over at 130°-145° C./3—4 mm. as a vis
cous, pale yellow oil in a yield of 180 g. The
pure compoundboiled at 135°-140° C./2~mm.
was obtained as a colorless oil boiling as 167°172° C./1-2 mm. in a yield of 125 g. The dicyclo
To a rapidly stirred, heated mixture of the
pentadiene in this preparation apparently de
polymerizes to supply cyclopentadiene which
above cyclopentadiene-safrol adduct (91 g.), 40
forms the adduct as indicated. ‘This method of
forming intermediates is a particularly useful
g. of water, and 40.5 g. of sodium thiocyanate,
maintained at 95° (2., there was added drop
wise 50 g. of. concentrated hydrochloric acid
and advantageous one.
(35%—37% HCl) during the course of ten min
v
The above compound (94 g.) was rapidly stirred
utes. The mixture was stirred at 95° ‘C. for one
hour after all the hydrochloric acid had been
with 35 g. of water and 32.4 g. of sodium thio
cyanate at 95° C. while 40 g. of concentrated 45 ‘added. The oily reaction product was taken up
hydrochloric acid was added dropwise thereto»
in benzene, the benzene solution ?ltered'and then
during the course of twenty minutes. After all
washed several times with water, dried, and dis
the acid had been added, the mixture was stirred
tilled in vacuo.
‘
The fraction boiling at 220"-230° CJZ mm. was
for one hour longer at 95° C., then cooled, taken I
a viscous, pale yellow oil. The yield was 86 g.
up in benzene, ?ltered, washed, dried, and dis
tilled in vacuo.
,
Y
.
Upon redistillation, it boiled at 214°-'216° C./1
'
'mm. The compound is an isothiocyanate having
The product boiling at_230°-240° C./1
was
a thick, pale vyellow oil ‘having vthe properties of
an isothiocyanate of the probable formula
the probable formula
'
C
Cali;
55
CH
_
c§l\cm
H,—-— -—cn;-<
_
l
H: i '
1£i=c=s
I
o
v
'
_ \C‘Hl
vo/e’
_
Example 8'
Ezample a
To a rapidly stirred mixture of 56.7 g‘. of sodium
thioeyanate, 60 g. of water‘, and 124‘ g. of 2,5‘
endomethylene-Aa-tetrahydro-benzylbenzoate a.
Amixture \ of .201 mg.‘ of ?-bromostyr'ene, and
as 83.4 g.- of- dicyclopentadiene washeated under
reflux at 160°-165° C. for seven hours, andthe
product distilledln vacuo, resulting I in aQcom
. pound having the formula ..
EsLJ‘iE-CFrfOQ -,
' maintained at 95298? 0., there was added drop_—_
2,41 1,889
8
The compound having the formula
which boiled at 131"7-140° C./6-7 mm. It was'a
pale yellow oil. The yield was 80 g.
‘
CH
A mixture consisting of 50 g. of the above com
pound, 24.3 g. of sodium thiocyanate, and 25 cc.
of water was rapidly stirred and heated to 95°
C. . To the'stirred, heated mixture, 30 g. of con
' centrated hydrochloric acid was added dropwise
during the course of forty minutes. The oily re
action product was taken up in benzene, the
benzene solution ?ltered, dried, and distilled in 10 was obtained as a colorless, viscous oil boiling at
vacuo.
'
155°-160° C./1 mm.
The product boiled at 210°-220° C./2 mm. and
A stirred mixture of 40 g. of the above 2,5.
was an isothiocyanate. It is a viscous, pale yel
endomethylene - AL tetrahydro-benzyl-trichloro
low oil having the probable formula
‘
phenyl ether, 16.2 g. of sodium thiocyanate, and
15 17 g. of water was treated dropwise at 95°-98°
on
I
C. with 20 g. of concentrated hydrochloric acid
during the course of thirty minutes.’ vThe mix
ture was then stirred one hour longer at 95° C.
and worked up as in Example 8.
20
The product boiling at 235°~240° C./1 mm. was
a very viscous, pale yellow oil having the proper
ties of an isothiocyanate of the probable formula
Example 9
or: _'
Helm
{
—
A mixture of 139 g. of dicyclopentadiene and
190 g. of allyloxydihydronordicyclopentadiene
was‘heated at 165°-l75° C. for ten hours under
re?ux condenser and the product distilled in
-
vacuo.
on
o{l\om
E Hi
n l
\ {
v
13K
-
Example 11
on,
A_ mixture of 104 g. of styrene and 139 g. of di
35 cyclopentadiene was heated under re?ux in the
presence of 5 g. of phenyl-p-naphthylamine for
a-om-o- H—-—‘-—— -- H
seven hours at 150°-170° C., and the product dis
C I
tilled in vacuo.
distilled over at 145°-150° C./l mm. as a colorless,
viscous oil.
01
1 '
N=C=S
o€l\o§
1 ii \cni
'
01
l on, J}
|
m-I- -c1zr-o_<
30
The compound having the formula
on
c§|\cm'
26
-
-
The desired product having the formula
40
0
Cafes
A rapidly stirred mixture of 58 g. of the above
compound, 24.3 g. of sodium thiocyanate, and 25
g. of water was treated at 95° C. with 30 g. of
was
concentrated hydrochloric acid, added dropwise 45
during ?fteen minutes. The mixture was then
stirred for forty minutes at 95° C. and diluted
boiling at 106°-110° C./7 mm. was collected in a
yield of 100 g.
with 500 cc. of water. The oil layer was taken
up in benzene, ?ltered, washed, dried, and dis
tilled in vacuo. The product boiling at 197°~203°
To a rapidly stirred mixture of 72 g. of the
C./1 mm. was a viscous, pale yellow oil having 50 above compound, 48.5 g. of sodium thiocyanate,
and 50 g. of water there was gradually added 60
the properties of an isothiocyanate of the prob
g. of concentrated hydrochloric acid at 90°-95° C.
during the course of thirty minutes. The mix
CH)
ture was thereafter heated and stirred for one
0
hour- at 95° C. and worked up by ?ltration, wash
ing, drying and vacuum distillation as described
Li.
in the previous examples.
The isothiocyanate having the probable for
poo
.
mula
The allyloxydihydronordicyclopentadiene used
above is a colorless oil boiling at 117°-119° C./ 12
mm. obtainable by reacting dicyclopentadiene
with allyl alcohol at 90° C. in the presence of 65
I
Q
boron tri?uoride or sulfuric acid as a. catalyst, as
described in copending patent application Serial
No. 476,640, ?led February 20, 1943.
Example 10
,was obtained, as a pale yellow oil boiling at
-70 159°-160° C./0.5 mm., in a yield of 77 g.
.
Example 12
A mixture of 46g. of dicyclopentadiene and 78
A mixture of 86 g. of dicyclopentadiene and
g. of allyl trichloro-(2,4,5) -phenyl ether was
1'73 g. of 5-ethyl-3-heptene-one-2 was boiled un~
heated under re?ux at 160°-l65° C. for eight
75 der re?ux at l62°-172° C. for seven hours and the
hours and the product distilled in vacuo.
2,41 1,869
9
.
.
ing the formula
l0
maintained at 83°-84°~ C. there was gradually
product distilled in vacuo. The compound hav
added dropwise 50 g. otconcentrated hydrochloric
I
acid-during the course of thirty‘minutes. .The
mixture was stirred for one-hall hour longer at
85° 0., then ‘poured into water and the benzene
layer separated, ?ltered, washed, dried, and dis
L
H-C 0—-CH:
tilled in vacuo.
.
'
.
The product boiling at 122°-125° C./0.5 mm.
was a colorless oil having the properties of an
isothiocyanate of the probable formula
distilled over 8,1} IMP-120° C./5-6 mm. as a color
less liquid.
A mixture of 59 g. of the above compound,
28.3 g. of powdered sodium thiocyanate and 100 g.
of benzene was rapidly stirred at 80°-85° C. while
35 g. of concentrated hydrochloric acid was added 15
dropwise thereto during the course of ?fteen
minutes. The mixture was stirred for one hour
longer at the boiling point, then washed, ?ltered,
dried, and distilled in vacuo.
'
Example 15
The product boiling at l'70°-l'l4° C./1 mm. was 20
a viscous, pale yellow oil havirfg the properties of
To a stirred mixture of 30 g. of ethanol, so g.
7 an isothiocyanate of the probable formula
of water, 28 g. of sodium thiocyanate, and 61.3.
of 2,5-endomethylene - Aa - tetrahydro dibenzyl
25
ether
‘
,
on
H:
Cara.
011,-,‘-- -0 0-0111
C
30'
Example 13
_
_
A mixture of 200 g. of eugenol and 169. g. of
maintained at 90° C. there was added dropwise
dicyclopentadiene was heated under re?ux for
35 g. of concentrated hydrochloric acid during
fourteen hours at 160°-l65° C. and the product 35 the course of twenty minutes. The mixture was
distilled in vacuo.
‘
then stirred thereafter for one and one-half hours
The desired compound having the formula
at 90°‘ C. and ?nally washed, ?ltered, dried, and
distilledinvacuo.
O OH:
J
‘
'
'
The product boiling at 184°~186° C./1.5 mm.
40' was a pale 'yellow oil having the properties of
an isothiocyanate of the probable formula
OH
-
e
on
distilled over at 147°-150° C./1 mm. as a pale
yellow oil which solidi?ed toa? crystalline mass. 45
Concentrated hydrochloric acid (30 g.) was
cg i\om
{Leaded-D"
Hr
added dropwise to a ‘rapidly stirred mixture con
sisting of 48.5 g.f of theabove cyclopentadiene
eugenol adduct, 50 cc. of benzene, 25 cc. of water,
-
ilr=c=s
.
‘
and 24.3 g. of sodium thiocyanate maintained at 60
85°~90° C. The mixture was heated for % hour
The 2,5-endomethylene-M-tetrahydro-dibenzyl
longer at 85° C.. then ?ltered, the benzene solu
ether used above is a colorless liquid boiling at
114°-118° C./0.5 mm. obtainable by boiling di
tion' washed;dried, and distilled in vacuo. ,
The isothiocyanate having the probable formula
cyclopentadiene with allyl benzyl ether;
'
55
Example 16
v
I
A mixture of 113 g. of ben’zyl allyl sul?de .and
96 g. of dicyclopentadiene'was heated six hours
at '16_O°-1'l0° C. and the product distilled in vacuo.
' The compound boiling at l40°-l50° ‘C./1-2 mm.
having the formula
boiled at 215L211;° c./1, mm.
thick oil.
~
Example 14. ~
65
To a rapidly stirred, heated mixture of 40.5 g.
oi’ sodium thiocyanate, 50 g. of water, 50 g. of
benzene, and 55 g. of 2,5-endomethylene-A3-tetra
\
hydrophenol
I
,
orr
cfl$cm
'
n
Hrv
'
'
l
11-01:
~
It was 9, ve
5
H-CHrB-oIrrG
I
-
-
>
——
.
70
was obtained as a pale yellow oil.
A mixture of 40 g. of the above compound.
40 g. of benzene, 40 g. of water. and 16.2 g. of
sodium thiocyanate was stirred rapidly at 84° C.
while 20' g. of concentrated hydrochloric acid
2,411,869‘
11
was added dropwise during ?fteen minutes.
The ‘
12
sodium thiocyanate, and 88.5 g. of 2,5-endometh-
ylene-A3-tetrahydro-benzyloxypropionitrile
oil layer was separated, washed, ?ltered, dried,
and distilled in vacuo.
The product boiling'at 210°-215° C./0.5 mm.
was a viscous, yellow oil having the properties of
an isothiocyanate of the probable formula
cg cn\
' cm'
CH1
The mixture was stirred 30 minutes longer at
the boiling point, then ?ltered and washed several
times'with water, dried, and distilled in vacuo.
i=e=s
The product boiling at 195°-205° C./1 mm. was a
colorless oil weighing 70 grams which gave tests
-, for an isothiocyanate of the probable formula
15
Example 17
1
A mixture of 136 g. of 2,5-endomethylene-A3
tetrahydro-6-methyl-benzaldehyde.
20
CH
H-CHO
25
(the adduct of cyclopentadiene and. crotonal
dehyde), 81 g. of sodium thiocyanate, 100 g. of
benzene, and '81 g. of water was rapidly stirred
at 85° C. while 100 g. of concentrated hydro
chloric acid was gradually added dropwise dur
Upon redistillation, the pure compound boiled at
200°-205° C./1 mm.
0
ing the course of .45 minutes. The mixture was
stirred thereafter for one hour longer at 87°C.,
dicyclopentadiene with B-allyloxypropionitrile.
then ?ltered, and the benzene layer washed,
dried, and distilled in vacuo.
The crude product boiling at 140°~l50° C./3
mm. amounted to 62 g. 'Upon redistillation, it
boiled at 118°-124° C./0.5 mm.
Example 18
A mixture of 40 g. of 2,5-endomethyleneiA3
tetrahydrobenzyl-sec, octyl ether.
CH
C{ l \CHI
CH:
CH:
The 2,5-endomethylene-A3-tetrahydro-benzyl
oxypropionitrile used above is a colorless oil boil
ing at 104°-108° C./1—2 mm. obtained by heating
The products of this invention are isothiocya
nates or mixtures containing said isothiocyanates
in which the isothiocyanate group is directly at
tached to a carbon atom of the saturated and re
' arranged ring obtained from the original cycle of
the cyclopentadiene.
I claim:
40
1. A method for preparing addition-rearrange
ment products of thiocyanic acid and cyclopenta
diene-mono-ole?nic adducts, which comprises re
acting said adducts with thiocyanic acid in the
45 presence of water, the thiocyanic acid being grad
ually liberated in the reaction mixture by the ac
CH\ I CH-CHr-O-(‘JH-(CHah-CH:
tion- of a non-oxidizing mineral acid upon a salt of
thiocyanic acid.
2. As new compounds, the reaction products ob
' 5o tained by the addition of nascent thiocyanic acid
in an aqueous medium to cyclopentadiene-mono
40 g. of benzene, 20 g. of water, and 16.2 g. of
sodium thiocyanate was rapidly stirred at 83° C.
while 20 g. of concentrated hydrochloric acid
was added dropwise during ten minutes. The
mixture was then stirred one hour longer at 83° “
0., ?ltered, the benzene layer separated, washed,
ole?nic adducts with consequent rearrangement
of the ring system of said adducts, said products
comprising isothiocyanates in which the isothio
cyanate group is directly attached to a carbon
atom of the saturated, rearranged ring obtained
from the cyclopentadiene.
'
,
dried, and distilled in vacuo.
The product boiling at 185°-190° c./2 rnm. ,
3. M newcompounds, addition-rearrangement
was a pale yellow oil amounting to 30 g. which,
products of thiocyanic acid and substances hav
upon redistillation, boiled at 170°~172° C./1 mm. “ ing the formula
and possessed the properties of an isothiocyanate
of the probable formula
CH
'
o
wherein R is an aromatic hydrocarbon nucleus,
Example 19 -
70 said products being isothiocyanates in which the
isothiocyanate group is directly attached to a car
bon atom of the saturated and rearranged ring
obtained from the cycle supplied by cyclopenta
diene in the preparation of said substances.
was added dropwise during one hour to a stirred
boiling mixture of 90 g. of benzene. 4.1 3. of 7o 4. As a new compound, an addition-rearrange
Fifty grams of concentrated hydrochloric acid
.
'
2,411,809
'
13
14
ment ‘product, of thiocyanic acid and a substance
having the formula
6. As a. new compound, an addition-rearrange;
ment product of thiocyanlc acid and a substance
CH
c{
having the formula
cm
6
L f iggcsom
\{
==
said'compound being an isothiocyanate.
'
>
flif'
10
5. As a. new compound, an addition-rearrange-j
ment product of thiocyanic acid and a substance
having the formula
‘
OH
v
?iglwojl:
said compound being an isotluocyanate.
sén\
'
if n-czu-oCF-ox
i
.
.
Sam compound be us an isomocyanat’e
'
HERMAN A. BRUSON.
I
0{ I \cm
v
. .
.
1.5
20
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