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P
i
1
3,060,198
TETRACYANUF
Claus D. Weis, Wilmington, Del“, assignor to E. I. du
Pont de Nemours and Company, Wilmington, Del, a
corporation of Delaware
N0 Drawing. Filed Get. 6, 1059, Ser. No. 846,070
1 Ciaim. (Ci. 260-3461)
y
3,060,108
..
Patented Got. 23, 1962
2
3.33%; N, 23.32%. Found: C, 39.73%; H, 4.12%; N,
22.49%.
The tetracarbethoxyfuran starting material Was obtained
by condensing ethyl sodiooxaloacetate in chloroform in
the presence of bromine to yield the ,B-ketDnic ester which
was then furanized with sulfuric acid to tetracarbethoxy
furan, as described in detail by Reichstein et al., Helv.
Chim. Acta 16, pg. 276 (1933).
p
This invention relates to novel heterocyclic compounds,
A sample (10 parts) of the crude tetracarbamoylfuran
and especially to novel heterocyclic compounds having a 10 was then dispersed in an excess of phosphorus oxychloride
plurality of cyano substituents directly attached to the
and re?uxed for 31/2 hours. The hot mixture was poured.
heterocyclic ring. More particularly, the invention re
onto ice, and after two hours the solid material was
lates to tetracyanofuran as a new compound, to a novel
?ltered oif. The solid was extracted with methanol, and
method for preparing the new compound, and to novel
the ?ltrate was decolorized with charcoal. On crystal
precursor compounds which are produced as intermedi 15 lization, the ?ltrate yielded colorless crystals, which, after
ates in the preparation of tetracyano-furan.
drying thoroughly with air melted over the range 123~4°
Tetracyanofuran is a derivative of furan wherein the 4
C. The product was identi?ed as tetracyanofuran. An
ring hydrogens are replaced with cyano groups. The
alysis of this product follows:
compound may be represented as follows:
Analysis.—Calcd. for C8N4O: C, 57.15%; N, 33.33%.
20 Found: C, 56.73%; N, 33.42%. .
EXAMPLE 11
oN-o
O
Preparation of Tetraeyanofnran from 2,5-Dicarbeth0xy
3,4-Dicyanofnran
The principal object of the present invention is to pre
A. Preparation of the disodium salt of diethyl 2,5-di0x0
pare tetracyanofuran. Another object of the present in 25 3,4-dicyanoadipate.-—To a dispersion containing 52 parts
vention is to provide a novel method for preparing tetra
of sodium hydride in 176 parts of benzene was added with
cyanofuran which is convenient and economical. A still
stirring 160 parts of diethyl oxalate, and the mixture was
further ob ject of the present invention is to prepare novel
warmed to 55° C. Without further heating, a solution
intermediate compounds which are useful, not only in the 30 of 40 parts of succinonitrile in 308 parts of benzene was
preparation of the tetracyanofuran, but which have in
added with stirring over a period of three hours. After
dependent utility in other connections as well. These
the addition was complete, the mixture was stirred for
and other objects will become apparent from a considera
one hour. Ether was added, and the bright yellow precipi—
tion of the ensuing speci?cation and claims.
fate was removed by ?ltration. The precipitate was dried
The foregoing objectives are achieved by the reaction 35 under vacuum. Analyses indicated the powder to con
of a tetra-substituted furan having at least two carbalkoxy
tain the disodium salt of diethyl 2,5-dioxo-3,4-dicyano
substituents with ammonia to prepare the corresponding
adipate.
carbamoyl compound which, in turn, is dehydrated with
B. Preparation of 2,5-dicarbeth0xy-3,4-dicyanofuran.~—
phosphorous oxychloride to produce the tetracyanofuran.
To a solution containing 64.8 parts of an impure sample
More speci?cally, the tetra-substituted furan starting ma 40 (containing about 50% by weight) of the disodium salt
terial has 2 to 4 carbaloxy ring substituents, the remaining
of diethyl 2,5-dioxo-3,4-dicyanoadipate, 213 parts of ether
ring substituents, where there are any, being cyano groups
and 0.5 part of pyridine was added, over a ?fteen minute
provided, however, that no cyano substituent is attached
period, a solution containing 24 parts of thionyl chloride
to a ring carbon atom directly adjacent to the oxygen
in 71 parts of ether. After the addition was complete,
atom of the furan ring. For example, a tetracarbalkoxy 4.5 the mixture was re?uxed for two hours.
furan or a 3,4-dicyano dicarbalkoxy furan may be re
acted with ammonia to convert the carbalkoxy groups to
carbamoyl groups. The intermediate compounds pro
duced in each instance may then be dehydrated to produce
2,3,4,5-tetracyanofuran.
A more complete understanding of the invention will
be gained from a consideration of the following ex
amples.
EXAMPLE I
Preparation of Tetracyanofuran from
Tetracarbethoxyfuran
The mixture
was ?ltered while still warm, and the residue was ex
tracted twice with ether. The combined extracts were
neutralized with an aqueous solution of sodium bicar
bonate, washed with water and dried over sodium sul
50 fate.
Evaporation of the ether yielded 20 parts of im
pure 2,5-dicarbethoxy-3,4-dicyanofuran.
Recrystalliza
tion from dilute ethanol gave 12.5 parts of white crystals
'of the compound which after drying melted over the range
86.5-87.5 ‘’ C. Chemical and spectrophotometric analyses
con?rmed its composition and structure.
Analysis.—Calcd. for C12H10N2O5: C, 54.96%; H,
3.85%; No. 10.74%. Found: C, 54.94%; H, 3.77%; N,
A mixture containing 150 parts of crude tetracar—
10.83%.
bethoxyfuran suspended in a lzl-by-volume solution of
C. Preparation of 2,5 - Dicarbamoyl - 3,4 -Dicyan0
methyl alcohol and concentrated ammonium hydroxide 60 furan.—A mixture containing 26 parts of the 2,5-dicar
was saturated with gaseous ammonia at ice-bath tempera
bethoxy-3,4-dicyanofuran dispersed in 135 parts of methyl
ture. After stirring for twenty-four hours, the solid prod
alcohol was treated with 75 parts of an aqueous 25%
uct was removed by ?ltration and washed successively
ammonium hydroxide solution. The mixture was then
with water, methanol, acetic acid and ?nally with meth
stirred for ?fteen minutes while being cooled in a cold
anol. The solid was dried over phosphorous pentoxide 65 water bath. The precipitate was ?ltered off and washed
and potassium hydroxide, giving 95 parts of dry product.
with ether. 2,5-dicarbamoyl-3,4-dicyanofuran was ob
The impure compound did not melt but became slightly
tained in good yield (15 parts). The compound did not
yellow about 280° C. and black at about 310° C. Chemi
:melt but slowly decomposed above 200° C. Chemical
cal and spectrophotometric analyses indicated the product
analyses and infrared examination con?rmed its com—
to contain 2,3,4,5-tetracarbamoylfuran. Analysis of this 70 position and structure.
product follows:
Analysis.-—Calcd. for C8H4N4O3: N, 27.45%. Found:
Analysis.-—Calcd. for C8H8N4O‘5: C, 40.44%; H,
N, 26.95% .
'
A
3,060,198
3
4-
B. Preparation of Tetracyanofuran.-A dispersion
.
groups, “X” and “Y” are both cyano groups.
containing 4.08 parts of 2,5-dicarbamoyl-3,4-dicyanofuran
and 6 parts of phosphorus oxychloride was treated with
10 parts of pyridine, and the mixture was stirred without
‘external "heat until the solid dissolved. Upon standing, 5
the entire mixture solidi?ed. Water was added (80 parts),
and after two hours, the solid residue was ?ltered off.
The solid was dried over phosphorus pentoxide, yielding
( 1) 2,5-dicarbamoyl-3,4-dicyanofuran:
2.78 parts of slightly brownish crystals. Charcoal de
"colorization and recrystallization from methanol gave 10
(2) 2,5-dicarbalkoxy-3,4-dicyanofuran:
NC—G-—C—CN
‘colorless crystals which after drying, melted over the
range 1'23-4" C. The product did not depress the melt
o
ing point of the tetracyanofuran obtained in Example I
o
Balk-O-iL-C
and the infrared spectra of the two samples were super
imposable.
Thus the
present invention embraces the following new compounds:
o
15
EXAMPLE III
Preparation of Tetracyanofuran from 2,3,4,5-Tetracar
bamoylfuran
A dispersion of 24 parts of tetracarbamoylfuran (pre 20
'pared as described in Example I) in 125 parts of phos
phorus oxychloride was heated at re?ux for three hours.
The excess phosphorus oxychloride was removed under
vacuum at ordinary temperatures and the residue was
decomposed with ice at such a rate that the temperature 25
did not exceed 15° C. The mixture was allowed to stand
an additional thirty minutes in an ice bath, and the light
C—(%——O—RArk
(3) 2,3,4,5-tetracyanofuran:
No-o—-—o-oN
N o-o
o
(4) 2,3,4,5-tetracarbamoylfuran:
yellow crystals which deposited were ?ltered oif. The ?l
vtrate was continuously extracted with ether for four
hours. Evaporation of the ether yielded a second crop 30
of yellowish crystals.
The crystalline fractions were
combined and dissolved in hot benzene, and the mixture
was ?ltered. Evaporation of the benzene gave 11.5
parts of colorless crystals, identi?ed as tetracyanofuran.
The product was puri?ed further by recrystallization sev
eral times from methanol. This product was identical
with recrystallized samples of the tetracyanofuran ob
tained in Examples I and II.
According to the present invention, it is possible to
prepare tetracyanofuran from a tetra-substituted furan 40
having at least two carbalkoxy substituents on the furan
ring. The tetra-substituted furan starting material may
have two, three, or four carbalkoxy substituents. If it,
has less than four of the latter, the remaining .substituent
l
(6) 2,4,5-tricarbamoyl-3-cyanofuran: V
NC--O—C—(%—NH2
HzN——C—-C
(l \O/
or substituents are cyano groups provided, however, that 45
Suitiable starting materials for the tetracyanofuran
no cyano group is attached to a ring carbon atom directly
synthesis of the present invention are the tetra-substituted
attached to the oxygen atom of the furan ring. The start
furans having at least 2 carbalkoxy substituents; the other
ing material is treated with ammonia to produce in each
instance the corresponding carbamoyl compound which
ring positions being occupied by either carbalkoxy or cyano
radicals. The carbalkoxy groups are preferably those
is then, in turn, dehydrated to obtain the tetracyanofuran. 50 of the lower alkyls such as carbomethoxy and carbo
v Tetracyanofuran is a new compound and its prepara
ethoxy radicals. Thus the tetracyanofuran may be syn
,tion is the principal objective of the present invention.
thesized from 2,3,4,5-tetracarbomethoxyfuran, 2,3,4,5—
Yap-ions of the intermediate compounds which may be
tetracarbethoxyfuran, 2,5 - dicarbomethoxy-3,4-dicyano
produced enroute to tetracyanofur-an in accordance with
furan, 2,5-dicarbethoxy-3,4-dicyanofuran, 2,4,S-tricarbo
the invention, however, are themselves new compounds 55 methoxy-3-cyanofuran, 2,4,5-tricarbethoxy-3-cyanofuran,
which in some instances, exhibit independent utility.
alkyl homologs of such compounds, and the like. If
Therefore, in the broadest sense, the new compounds of
desirable, however, the novel compounds of the present
the present invention may be represented by the follow
invention which contain carbalkoxy radicals may also be
ing generic formula:
prepared with the higher alkyl radicals having three or
60 more carbon atoms. Generally speaking, therefore, the
precise nature of the alkyl radical in the carbalkoxy-sub
stituted furans is in no sense critical to the invention.
The ammonolysis of the carbalkoxy-substituted furans
maybe conveniently carried out in an ammoniacal aqueous
wherein “X” and “Y” are each either cyano, carbalkoxy, 65 methanol medium. Such an ammonolysis medium o?ers
or carbamoyl ‘groups; “R;" and “R2” are always alike
the advantage of acting as a solvent for the starting ma
and {are likewise either cyano, carbalkoxy or carbamoyl
terial while at the same time providing a reaction medium
groups; provided, however that when “R1” and “R2” are
from which the intermediate carbamoyl products precipi
carbalkoxy groups, “X” and “Y” are either both cyano
tate as insoluble products. The latter is thus obtained
radicals or one of them is a cyano radical and the other 70 in a relatively pure form eliminating the necessity of pro
is a carbalkoxy group; provided further that when “R1”
viding cumbersome and costly puri?cation steps. Other
and “R2” are carba-moyl groups, “X” and “Y” are either
ammonolysis procedures may be used, however, and in
this connection the ammonolysis may be carried out in
both cyano radicals, both carbamoyl groups, or one is
a cyano radical and the other'is a carbamoyl group; and
various other media such as aqueous ammonia, anhydrous
provided further that when “R1” and “ 2” are both cyano 75 methanolic ammonia and the like.
3,060,198
5
operable, however, although temperatures should be main
tained below the decomposition temperatures of prod~
The time required for the ammonolysis of the carb
alkoxy-substituted furan compounds depends not only
upon the choice of reaction medium but also upon the
particular reactants and the reaction products in each
instance. Reaction times may thus vary anywhere from
ten minutes to ten hours, or longer. Generally, it has
not and/ or reactants.
Tetracyanofuran is a colorless, crystalline compound,
useful in the preparation of a number of valuable prod
ucts. For example, tetracyanofuran reacts with Z-amino
been found that as carbalkoxy groups on the furan ring
benzothiazole, in la one-to-four molar proportion in tri
chlorobenzene at 155° C. to produce a yellow-green pig
are replaced by cyano groups shorter reaction times are
required; for example, of the order of ten to thirty min
ment. The pigment is insoluble in all common reagents
utes for the dicyanodicarbalkoxy compounds. The tetra 10 and absorbs strongly in the visible spectrum with three
carbalkoxyfurans are less reactive and, even in the
maxima in the 400-450 millimicron range. The pigments
aqueous ammonolysis media, generally require six hours
‘and a suitable method for their preparation, are fully de
or more for complete reaction. Ammonolysis usually
proceeds more rapidly in aqueous reaction media than in
scribed in copending application, Serial No. 846,071
anhydrous systems.
?led October 6, 1959, in the name of Howard E. Sim
15 mons, and having a common @assignee with the present
The ammonolysis reaction is preferably carried out
within the temperature range of 0-50° C., although the
reaction proceeds at temperatures of —-10° C. or lower.
The desired temperatures are usually maintained by cool
invention. Tetracyanofuran also forms pigments with
phenylhydrazines. Reduction of tetracyanofuran pro
vides polyaminofurans, useful as curing agents for epoxy
resins. The amines also react with dibasic ‘acids such as
ing the reaction vessel in ice or cold water. Temperatures 20 adipic or sebacic acids to produce polyamides. The carb
greater than 50° C. may be used if desired, i.e. moderate
alkoxy and dicyanodioarblamoyl furans, in ‘addition to
temperatures up to about 100° C. although at higher
being useful as intermediates in the synthesis of tetra
temperatures the reaction proceeds very rapidly and is
cyanofuran, have other valuable applications. The carb
lalkoxy compounds are useful in the preparation of poly
25 esters by ester interchange with alcohols such as ethyl
uct.
The polycarbamoyl products are readily converted to
ene glycol. Tetracyanofuran also is an effective fungicide
the corresponding polycyano compounds by dehydration.
against early tomato blight and is useful as an insecticide,
A suitable dehydrating agent is phosphorus oxychloride.
especially in the control of mites.
The amount of the phosphorus oxychloride employed for
The invention has been described in the foregoing
the reaction is not critical. When large excesses are em 30 speci?cation. It will be readily apparent to those skilled
di?icult to control leading to loss of some of desired prod
ployed, the oxychloride serves both as a dehydrating
agent and an active solvent for the product. After the
reaction has progressed to completion the excess reagent
may be removed by distillation under vacuum. Stoichi
in the art that many variations may be made in the pro
cedures and compositions described without departing
from the spirit of the invention. I intend, therefore, to
be limited only by the following claim.
ometric quantities of the oxychloride, i.e., one mole of 35 The compound of the formula
phosphorus oxychloride per carbamoyl group, are also
operable in the process without detriment to the product
|
yield. Inert diluents may be employed, too. In the ab
sence of an active solvent for the product, the tetracyano
0
furan may be recovered from the reaction mass by se
lective extraction.
It is within the scope of this invention to employ in
the dehydration step of the process reaction accelerators
such as pyridine. The polycarb-amoyl compounds tend
to dehydrate rather slowly, and accelerators, such as 45
pyridine, to speed up the dehydration will be useful
(though not required) in many instances. One mole of
pyridine for each mole of hydrogen chloride produced in
the reaction is preferred. Although smaller quantities
are permissible, large excesses of pyridine are to be 50
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,745,845
Jones et a1. _________ __ May 15, 1956
2,769,818
2,772,295
2,799,697
2,802,857
2,834,789
Schlesinger __________ __ Nov. 6,
Burness _____________ __ Nov. 27,
Maxion _____________ __ July 16,
Kesslin et a1. ________ __ Aug. 13,
Clausson-Kaas ________ __ May 13,
The dehydration reaction takes place at slightly ele
vated temperatures, and although the reaction is some
what exothermic, it is usually desirable to apply external 5
heat. Preferred reaction temperatures are within the
range, 50-110u C. Higher and lower temperatures are
1957
1958
OTHER REFERENCES
avoided to prevent undesirable side reactions involving
the cyano group.
1956
1956
1957
Degering: An Outline of Nitrogen Compound (1950),
p. 504.
Wagner et al.: Synthetic Organic Chemistry (Wiley,
1953), p. 596.
Schmidt: Organic Chemistry (7th ed. 1955), pp. 224
and 35 34.
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