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Патент USA US3071593

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[ice
1
3,971,583
Patented Jan. 1, 1963
2
starting materials for the processes of the invention are
3,071,583
aldehydes of the formula
POLYENE ALDEHYDE DERIVATIVES 0F
RHODANINES
Balthasar Hegedus, Binningen, Switzerland, assignor t0
Hoifmann-La Roche Inc., Nutley, N.J., a corporation of
New Jersey
No Drawing. Filed Nov. 15, 1960, Ser. No. 69,291
Claims priority, application Switzerland Nov. 20, 1959
8 Claims.
(Cl. 260-440)
.
'
(III)
wherein the bond indicated by dots may optionally be
The present invention relates to a procedure for the
hydrogenated, the symbol in represents a whole number
preparation of novel, intensely colored derivatives of
polyene aldehydes, particularly of such aldehydes which
from 0 to 3 and the symbol n represents 0 or 1, the sum
of m and n being at-least 1.
contain more than two unsaturated linkages.
The processes of the invention comprise reacting a
Exemplary of suitable compounds of the above formula
polyene aldehyde containing at least two ‘unsaturated linkf
are such‘ polyene a'ldehydes as:
ages with a rhodanine of the formula
4,9, 1 3 -trimethyl- 15 - (2, 6, 6-trimet-hyl- 1 -cycl0hexen-1-yl)
2,4,8, 1 0,12,141pentadecahexaen-6-yn-l-al.
2,6,1 1, 15 -tetramethyl-1 7- ( 2, 6,6-t1imethyl-1-cyclohexen
20
2,6,10,15,19-pentarnethyl-21-(2,6,6-trimethyl-1-cyclo
hexen-1-yl)-2,4, 6,8,10,12,14,16,18,20-heneicosadecaen
(I)
25
wherein the symbol R1 represents hydrogen, alkyl, aryl
or aralkyl. Preferably, R1 represents hydrogen, lower
alkyl (such as methyl or ethyl), phenyl or benzyl;
l-al.
4,8,12,17,21-pentamethyl-23-(2,6,6-trimethyl-1-cyclo
hexen-l-yl)-2,4,6,8,10,12,14,16,18,20,22-tricosaun
decaen~1-al.
‘
Suitable starting materials for the process of the inven 30
formula
tion include, for example, polyene *aldehydes of the
’
2,6, 10, 14, 19,23 4hexamethyl-25l (2,6,6-trimethyl- 1-cyclo~
hexen-l-yl) 2,4, 6, 8,10,12, 14,1\6,18,20,22,24-penta
tcosadodecaen-l-al.
Finally, " vitamin-A-aldehyde, and derivatives thereof
which have the same carbon skeleton, can be employed
as starting materials. ‘In all of the above mentioned
CHO
OH;
1-y1)-2,4,6, 8,10,12,14, l6-heptadecaoctaen-1-al.
4, 8, 13, 17-tetramethyl-19-(2,6,6-trimethyl-l-cyclohexen
1-yl)-2,4,6,8, 12, 14, 16,18~nonadecaoctaen-10-yn-1-al.
polyene aldehydes, the ‘double bonds can be replaced in
CH3
part by triple bonds. ,
a
Representative of rhodanine ‘compounds suitable as
starting materials for the process of the invention are,
wherein R2 represents a hydrocarbon radical having the
carbon skeleton of geraniol or cyclogeraniol; and the 40 for example, compounds of Formula I above in which the
symbol R represents hydrogen, phenyl, methyl or benzyl.
The reaction of the polyene aldehyde reactant with the
symbols m and n represent the numbers 0 or 1, at most
one of these ‘symbols being 1.
As representative examples of such aldehydes, the fol
lowing compounds can be mentioned:
2-methyl-4- (2, 6, 6-trimethyl- l-cyclohexen- 1 -yl ) -2—buten
rhodanine reactant is advantageously effected in a water
misci-ble solvent, e.-g. alcohol or dioxan, in the presence of
45 ammonia or a low molecular weight organic base, eg.
diethylamine, diethanol-amine or triethylamine. In order
to obtain ‘good yields, it has been found desirable to in
clude water in the reaction mixture. A further increase
in yield can be obtained by addition of ammonium chlo
l-al.
2-methyl-4-(2,6,6-trimethyl-Z-cyclohexen-1~ylidene)~2
ibuten-l-al.
2-metl1yl-4- ( 2, 6, 6-trimethyl-1, 3 -cyclohexadien-1-yl) -2
buten-l-al.
ride.
The new polyene derivatives obtained by the processes
of the invention can be represented collectively by the
2-methyl-4-(2,6,6-trimethyl-1-cyclohexylidene)-2
formula
buten-l-al.
2, 6, 10'trimethyl-2,4,9-undecatrien-1—al.
4-methy1-6- (2, 6, 6—trimethyl- l-cyclohexen- 1 -y1) -2,4
hexadien-l-al.
4-methyl-6-(2,6,6-trimethyl-1~cyclohexylidene)-2,4
hexadien-Lal.
2, 6-dimethyl-8- ( 2, 6, 6-trin1ethyl-2-cycl0hexen- l-ylidene) 2,4,6-octatrien-1-al.
,
2,6-dimethyl-8- (2,6,6-trimethyl- l-cyclohexylidene ) -
2,4,6-octatrien-l-al.
An additional ‘group: of compounds especially suited as
60
wherein the symbol R1 represents hydrogen, alkyl, aryl,
or aralkyl (preferably hydrogen, lower alkyl, phenyl or
benzyl); and R4 represents the residue remaining after re
moval of the oxygen atom of the aldehyde employed.
These derivatives are characterized by their especially
3,071,583
3
4
intense coloring effect, and are useful as coloring agents
in the foodstuff, feedstutf and cosmetic industries. Addi
tionally they can be employed as antifungal agents.
The invention is further disclosed in the following ex
amples, which are illustrative, but not limitative, thereof:
Example 1
2.84 g. of 3,7-dimethy1-9-(2,6,6-trimethy1-l-cyclohexen
l-yl)-2,4,6,8-nonatetraen-1-al is re?uxed for two hours
consisting of hydrogen, lower alkyl, phenyl and benzyl,
R2 represents a hydrocarbon radical having the carbon
skeleton of a member selected from the group consisting
of geraniol and cyclogeraniol and each of m and n rep
resents a number from 0 to l, at most one of mi and n
being 1.
2. A compound of the formula
with 1.33 g. of rhodanine in a mixture of 95 ml. of alco 10
hol and 5 ml. of concentrated ammonia with addition
of a solution of 0.1 g. of ammonium chloride in 1 ml. of
water. The reaction mixture is allowed to cool to room
\ .1.
temperature and the precipitate which forms is ?ltered
....n
off, and washed with alcohol, ether and petroleum ether. 15
In this way, ‘there is obtained 3,7-dimethyl-9-(2,6,6-tri
methyl-l-cyclohexen-l-yl)-1-[thiazol-4(5H)-one - 2(3H)
wherein R1 represents a member selected from the group
thion-S-ylidene]-2,4,6,8-nonatetraene, of M.P. 216-217°
consisting of hydrogen, lower alkyl, phenyl, and benzyl;
which is colored black-violet.
R2 represents a member selected from the group consist‘
Example 2
ing of
When employing 2-methyl-4-(2,6,6-trimethyl—l-cyclo~
hexen-l-yl)-2-buten-l-al as the polyene aldehyde, but
otherwise under the same conditions as in Example 1,
there is obtained, after washing the ?lter residue with 25
alcohol and petroleum ether, 2-methyl-4-(2,6,6-trimethy1
and
l-cyclohexen-l-yl)-1-[thiazol-4(5H)-one-2(3H) _ thion
5-ylidene]-2-butene, of M.P. l40—142°, which is colored
light orange.
Example 3
30
l
Starting from 2,6-dirnethyl-8-(2,6,6-trimethyl-2-cyclo
hexen-l-yl)-2,4,6-octatrien-1-al, there is obtained, by pro
ceeding as indicated in Example 1, 2,6-dimethyl-8-(2,6,6
trimethyl-l-cyclohexen-l-yl)—l-[thiazo1-4(5H)
\
- one - 2
(3H)-thion-5-ylidene]-2,4,6-octatriene, of M.P. 204
206°, which is colored orange-red.
Example 4
Starting from 2,6-dimethyl-8‘(2,6,6-trimethyl-2-cyclo
hexen-l-ylidene)-2,4,6-octatrien-1-al, there is obtained,
by proceeding according to the indications in Example 1,
35 m represents a member from 0 to 3; and n represents a
member from 0 to 1, the sum of my and n being at
least 1.
3. 3,7-dimethyl-9- (2,6i;-6-trim'ethyl~1-cyc1oh'eb(en-1-yl) 1-[thiazo1-4-(5H)-one-2-.(3H)-thion-5-ylidene] - 2,4,6,8
40 nonatetraene.
4.
2-methyl-4-(2,6,6-trimethyl-l-cyclohexen - 1 - yl)-1
2,6-dimethy1-8-(2,6,6-trimethyl-2-cyclohexen-1 - ylidene)
[thiazol-4( 5 H) -one-2 ( 3H) -thion-5 -ylidene] -2-butene.
1-[thiazol-4(5H)-one-2-(3H)-thion-5-ylidene]-2,4,6 - oc
5. 2,6-dimethy1-8-(2,6,6~trimethyl-l-cyclohexenl - 311)
1-[thiazol-4(5H)-one-2(3H)-thion-5-ylidene] - 2,4,6-oc
tatriene, of M.P. 224-226“, which is black-violetin color.
tatriene.
Example 5
Starting from 4,9,13-trimethyl-15-(2,6,6-trimethyl-1
6. 2,6-dimethyl-8~(2,6,6-trimethy1-2-cyclohexen-l-ylid
ene)-1-[thiazol-4(5H)-one-2(3H)~thion-5-ylidene] - 2,4,
cyclohexen-l-yl) -2,4,8,10,l2,14 - pentadecahexaen-G-yn
6-octatriene.
l-al, there is obtained, by proceeding according to the
indications in Example 1, 4,9,13-trimethyl-15-(2,6,6-tri 50
yl)-1-[thiazol-4(5H)-one-2(3H)thion-S-ylidene] - 2,4,8,
methyl-l-cyclohexen-1-yl)-1-[triazo1-4(5H)-oue - 2(3H)
10,12,14-pentadecahexaen-6-yne.
8. 2,6,11,15-tetramethy1-17.-(2,6,6 - trimethyl-l-cyclo
thion-5-ylidene]-2,4,8,10,12,14-pentadecahexaen - 6 - yne,
of M.P. 210-211°, which is colored deep violet-red.
Example 6
hexen-l-yl)-1-[thiazol-4( 5H)-one-2( 3H) '- .thion - 5 - ylid
ene] -2,4,6,8,l0,12,14,16-heptadecaoctaene.
Starting from 2,6,1l,1S-tetramethyl-17-(2,6,6-trimeth
References Cited in the ?le of this patent
UNITED STATES PATENTS
yl-l-cyclohexen-l-yl) - 2,4,6,8,10,12,14,16 - heptadecaoc
taen-l-al, there is obtained, according to the indications
in Example 1, 2,6,1l,15-tetramethyl-17-(2,6,6-trimethyl
l-cyclohexen-l-yl)-1-[thiazol-4(5H)-one - 2( 3H) - thion— 60
‘5-y1idene]-2,4.,6,8,10,12,14,16-heptadecaoctaene, of M.P.
184—185°, which is colored deep red-violet.
7. 4,9,13-trimethyl-l5-(2,6,6-trimethyl-1-cyclohexen-l
2,907,761
2,990,430
Benton ___,_ ________ __'___ Oct. 6, 1959
Stern _______________ __ July, 27, 1961
OTHER REFERENCES
Turkevich et -a1.: Ukrain. Khim. Zhur., vol. 16, pages
I claim:
1. A compound of the formula
558 to 562 (1,950).
'
Brown et al.: Industrial and Engineering Chemistry,
vol. 46, pages 1508-12 (1954).
CH3
llR1
wherein R1 represents a member selected from the group
'
a .
Richter et al.: Journ. fiir Prakt. Chem.,.vo1. 7 (4th
series), pages 184-90 (1958).
70
Ried et al.: Annalen der Chemie, vol. 622, pages 37
42 (1959).
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