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Патент USA US3093687

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Unitcd States Patent O??ce
3,093,677
Patented June 11, 1963
I
2
replaced both in the diazo reaction and in that of this
‘
"
'
3,093,677
'
invention.
AROMATIC HALOCARBYL CHEMICAL PRODUCTS
Elmore L.’ Martin, Wilmington, DeL, assignor to E. I.
du Pont de Nelnonrs and Company, Wilmington, Del.,
. .a corporation of Delaware
7
'
The de?nition of Q ?ows ‘from the fact, evident be
low, that the compounds
. .
No Drawing. Filed Aug. 28, 1959, Ser. No. 836,601
13 Claims. ((21. 260-465)
‘I‘his invention relates to new dyestu?s and to their
have the ‘same capacity for coupling with color formers
(i.e., QI-I cmnpounds) as dorthe aryl diazonium salts.
The coupling reactions of the aryl d-iazonium salts are
well known and are discussed in detail by K. H. Saunders
in “The Aromatic Diazo Compounds and Their Techni
cal Applications,” Edward Arnold & Co., London (1949),
See. Ed., pp. 194-221. See also H. A. Lubs, “The
7 The rapid advances which have been made in textile
focused attention on the need to provide
dycstu?s which are light and wash-fast, which cover all or
was = re ‘a the entire visible spectrum, and which can be
applied to natural ?bers and to the newer synthetics with 15 ‘Chemistry of Synthetic Dyes and Pigments,” Reinhold
minim,
of application variations. The provision of such
Company, New York (71955), Sec. Ed., pp.
d --= ~ c: has been a long standing research objective,
-
l.
tonow has remained unattained.‘
The de?nition of QR is based speci?cally on the ability
of the present invention is, consequently,
to couple with benzene diazonium chloride partly be
provision of certain novel and useful dyestuffs.
20 cause diazonium chloride is the simplest and most readily
Another obiect of the invention is provision of a proc
‘available of the aryl diazonium chlorides and partly be
An,
ess for making the aforesaid novel dyestu?s.
In the ‘furtherance of the composition of matter as
pects of the invention, there is now provided a new class
of dyestu?s corresponding to the formula
cause such a de?nition points out that hydrocarbon com
pounds such as benzene and monoalkoxy benzenes are not
included among the color formers. ' Benzene and anisole,
25
for example, will react with certain highly activated aryl
diazonium halides but not with benzene diazonium chlo
ride to yield azo dyes.
The test to determine reactivity with benzene dlazonium
"chloride may be conducted as follows:
in which X1 and X2 individually or together are perhalo 30
Benzene diazonium chloride is prepared by treating
carbyl and oxoperhalocarbyl; Y is a negative or electron
one molar equivalent of aniline with 2.7 molecular equiv
attracting group; and Q is a color-forming group, i.e.,
alents of hydrogen chloride as a concentrated aqueous
a monovalent organic radical such that the correspond
solution. This solution is cooled to 0° C. and treated
ing QH compound is capable of condensing with benzene
with one molecular equivalent of sodium nitrite, dis
35
diazonium chloride to form an azo dye.
solved in twice its weight of water. The addition of the
More detailed de?nitions of the symbols of the above
nitrite solution is carried out at a rate so that the tem
formula are as follows:
'
perature does not exceed 5° C. To ten milligrams of
(a) X1 and X2, alike or dilferent, are separately,
compound QH dissolved in one to two ml. of acetone
monovalent perhalocarbyl or oxoperhalocarbyl radicals 40 there is added about 0.25 g. of sodium acetate. One to
of generally no more than 12 carbons or, joined to
three drops of the diazonium solution are then added to
gether, divalent perhalocarbyl or oxoperhalocarbyl radi
‘the test mixture. When QI-I contains an electron-donat
eels of generally 2-6 carbons forming with the depicted
ing group or is an'active methylene compound, the addi
carbons a carbocyclic ring of 4~8 carbons. Any oxo
tion of the benzene diazom'um chloride causes immediate
carbonyl oxygen present is carried by a carbon joined to 45 formation of an azo dye ranging in color from deep
one of the depicted doubly bonded carbons.
orange through red-purple to green. An alternative
“Pcrhalocarbyl” as used herein refers to organic radi
method for expressing the result is that there is formed
cals composed solely of carbon and halogen. “Oxoper
an azo compound having at least one absorption peak
halocarby ” refers'to organic radicals which contain otdy
between 350 and 750I millimicrons.
carbon, halogen, and oxocarbonyl oxygen. Exemplary 50 . QH compounds usefully ernployable in the present in
perha-iocarbyl radicals are perchloro- and per?uorcethyl,
vcntion are of two kinds, namely (1) those aromatic
perchloropropyl, perbromomethyl, periiuorodecyl, per
compounds containing electron donating groups and (2)
compounds containing active methylene groups.
In preferred QH compounds, Q may be R2NAr-,
chlonoisobutyl, periluorotrimethylene, perchlorotetrameth
ylene, l,l,4,4 - tetra?uoro - 2,3 - dichloro - 2 - butenylcne,
and the like. Exemplary oxoperhalocarbyl radicals are 55 ROONHNRAr-w RCH===NN—-RAI—,’
2,2,3,3,3 - pentachloropropionyl, 2,3 - dichloro - 1,4
dioxo - 2 - ibutenylene, perchloroadipoyl, perchloroacetyl,
per?uorosuccinyl, and the like;
(b) Y is an elecnonegative radical of the group con
sisting of cyano, nitro, alkylsulfon-yl, alkarylsulfonyl,
arylsulfonyl, aralkylsulfonyl, carboxy, alkoxycarbonyl,
carbamyl, halocanbonyl and acyl (i.e., alkylcarbouyl),
60
OH—— and
R0
all of generally no more than 12. and preferably no more
than 8 carbons; and
(c) Q is a radical that may
de?ned in terms of the 65 in which Ar is arylene; R and R" are hydrogen or hy
compound QH from which it is derived. QH is any or- , . drocarbyl; R’ is hydrocarbyl, beta-alkoxyethyl, beta-acyl
garlic compound capable of condensing with benzene di~
azonium chloride with the replacement of the depicted
oxyethyl, beta-cyanoethyl, or beta~trialkylammonium
ethyl; B and B’ are --CN, -—COOR, —COR, —CONR3,
hydrogen to form an azo dye. Q may thus be broadly
—CSNR2, --SO2R, --NO2, —'NR3+, and —SR=+; D is
de?ned as the monovalent radical or residue of a com 70 alkyl, halogen, ~SO3Na, or B; D’ is hydrogen or D, with
pound QH which reacts with benzene diazonium chlo~ . the proviso D’ and R" taken together may form another
ride to form an azo dye.
The same hydrogen may be " aryl ring; and n is 0 or i. In a given compound the sev
3,093,677
4
It is convenient, but not necessary, to etfect the reac
eral embodiments of R and R’ that may be involved may
tion between compound
be the same or different.
Aryl and arylene refer, respectively, to monovalent and
A-—O=C-Z
to divalent aromatic radicals. In the latter the divalency
stems from different carbon atoms. Among the aryl and
1'0 X:
and compound MY and QH in a reaction medium inert
arylene radicals are included those ‘from which the cor
to the reactants and to the products. Suitable media are
responding aromatic compound obtained by placing hy
aliphatic and aromatic hydrocarbons, dialkyl ethers,
drogen at the respective bonds of the aryl or arylene
group has a resonance energy of not less than 20 kcal./
mole. Resonance energies of organic compounds and the
10
determination of resonance energy is shown by Linus
anthryl, phenanthryl, benzpyryl, trypticyl, furyl, thienyl,
methylformamide, N-rnethyl-Nethylacetamide, N,N-di
methylacetamide, N,N - diethylacetamide,
Pauling in “The Nature of the Chemical Bond,” Sec. Ed,
Cornell University Press, 1945, pages 132-139.
Aryl groups particularly suited are phenyl, naphthyl,
cyclic esters, e.g., dioxane and tetrahydrofuran, N-alkyl
acylamides, e.g., dimethyl- and diethylformamides, N
N - methyl
formanilide, etc., tetramethylurea, tetraethylurea, pyri-»
dine, dimethylsulfoxide, acetonitrile, etc., nitrosodi
In general, the inert
15 methylamine, and tri?uoroethanol.
medium is used to facilitate the dissipation of heat from
pyrrolyl, and the corresponding arylene groups phenyl
ene, naphthylene, anthrylene, furylene, thienylene, and
the slightly exothermic reaction.
As previously stated, M in MY is a metal, preferably
pyrrolylene.
Hydrocarbyl refers to any monovalent organic radical
an alkali metal such as sodium, potassium, and lithium.
alkaryl, single ring, multiple ring, straight chain,
other alkali metals.
The temperature at which the reaction is carried out
MY compounds in which M is sodium are generally used
composed solely of carbon and hydrogen. The hydro 20 because
of the lower cost of sodium as compared to the
carbyl groups can be alkyl, cycloalkyl, aryl, aralkyl,
branched chain, large or small. The widest variation
does not detract from the fundamental characteristics of
the hydrocarbyl radical of passing unchanged in the proc
can be varied widely, e.g., from below —10° C. up to
25 the decomposition temperature of the reactants or prod
ucts. As a rule, the best results from the standpoint of
product yield and reaction rate are achieved at tempera
tures of from 0° C. to 100“ C. and this range embraces
20 carbon atoms are most available and to that extent
the conditions most generally used. Pressure is not a
are preferred. There is no question of the operability of
critical variable and ambient atmospheric pressure is gen
30
and the intent to include and disclose all hydrocarbyl
erally used for convenience, although pressures above or
groups whatsoever.
below can be employed, if desired. The time of the re
QH compounds containing an active methylene group,
action is dependent upon the particular reactants em
e.g., BB'CH—-, above, are those compounds which con
ployed and can vary up to one hour or more.
tain the methylene group adjacent to two carbonyl or
Complete reaction between compound
ess by which the products of this invention are made. In
general, hydrocarbyl groups containing not more than
other strongly electron-attracting groups. This methyl 35
ene group is discussed by Saunders, op. cit., pp. 207
217, is mentioned by Lubs, op. cit., pp. 101 and 102, and
is well known to workers in the azo dye art as a site of
coupling reactions.
Compounds containing active
and compounds OH and MY, of course, requires the
the present invention is through the active methylene
of one or other of the reactants have little value in im
methylene groups are at least partly aliphatic in nature. 40 use of at least equimolar quantities of each reactant.
When the active methylene group is adjacent to a car
This fact, however, in no way limits the molar propor
bonyl group, the compound is capable of existing in the
tions of these reactants and the relative amounts of each
can be varied widely. Generally the use of a large excess
tautomeric keto~enol form. Coupling in the process of
45 proving product yield. For that reason, approximately
group, one of the hydrogens being substituted.
equirnolar quantities are usually employed.
The process aspects of this invention may be illustrated
Exemplary compounds of the formula
schematically as follows:
50
usable in the process of the invention are shown in Table
I. Exemplary intermediate compounds of the formula
In these equations A and Z are halogen of atomic num.
A—O=O—Y
her 9 through 35, i.e., ?uorine, chlorine, or bromine; 55
it in
Q, X1, X2, and Y have the previously-indicated meanings;
are shown in Table II.
and M is a metal, preferably an alkali metal such as sodi
um or potassium.
TABLE I
The process of the invention may be accomplished
simply by adding the various starting materials together
and separating the resultant colored product by obvious
(I)
Ol-0=C—Cl
means. There are no particularly critical process varia
(ID
or,
01,
Br~o=0-Br
bles involved. It is to be understood, however, that the
F:
F3
intermediate product
A—C=C—Y
65
2'0 XI
(In)
need not be isolated, i.e., the process can be carried out
by mixing all of the reactants initially. Likewise, if de
sired, intermediate
70
(IV)
A-C=O—Y
(V)
can be prepared separately and then reacted in a separate
75
F;
0-131
01.
01:
Cl]
Oh
Cl]
013
o1-o=o-o1
or
1i. .
operation with compound QH.
Br-O
F:
or
o1-o=o-o1
001
001
8,093,677
(VI)
(XXII)
(VII)
Fr
—Fl
(XXIII)
0
I
F:
15 (XXIV)
(13-)
01-0
=0
IS=0
F
F F
F
F
F
F
'
F
20
(XXV)
F
(X)
25
(X1)
30
01
O1
01
G1
I
aixvn
(XII)
35
OKIII)
(I)
(XIV)
45
(XV)
50
an},
(IV)
(XVI)
(ti/$101 01/5101
61
55
QV)
WI)
A]
(XVII)
WEB
(XV III)
65
F1
(xxx)
(X)
70
(Xx)
(XI)
(XXI)
75
Fl
3,093,677
7
our)
8
Cl-O=O--SO|OnH¢—CH|(P)
°= \ / =0
\ /0
(P)CHI—CBHQ:S/
O
——-—~G—CsHcN (CHI )
01/ \Ol
(x111)
5
0=$
Ol--C=O—NO|
/0=0
01/ \Ol
Oh- -—-O—-0h
(XIV)
(IV)
Cl—C=C-—s0:OH|CBH5
F:-
=0
\/
10
—-F:
0
A solution of 2.34 g. of tetrachlorocyclopentene-L3
it,
dione (I), prepared as described ‘in I. Am. Chem. Soc.
Representative usable QH compounds of the aromatic 15 78’ 489 09,56)’ m 25 cc‘ 0? dunethylformamlde was
type are: Z’GdimethYlPhenol; 1_acetyl_2_methyl_2_pheny1_
cooled to’ 15 C. 'I'o the solution there was added 2.4 g.
hydrazine; sodium l-naphthol-Z-sulfonate; N-allyl-N-
of N’N'd‘methylamlme (11,1)! followed by 1'8 g- of ?nely
methylaniline; N,N - dibenzylaniline; N - cyclohexyI-N-
‘Powdered anhydrmfs, sodium P91118116 sul?naw (H)
methylaniline; N-methyl-N-propargylaniline; N,N.diethy1-
'I‘hroughout the addition of the sodium p-toluenesul?nate
alpha-naphthylamine; N,N - di(beta- ethoxyethyDaniline; 20 the timperamm of the "m0" manure was k613i 9* 15
N,N-di(beta-acctoxyethyl)aniline; N,N-dimethy1aniline;
to 20' C. by means of external cooling. {After stlrrmg for
N,N-dioctadecylaniline; N - (beta - benzoyloxyethyl)-N-
19 mum“? ‘at 15° i0 20' C» the reaO?On mixture was
methylaniline; 3-mcthylsalicy1amide of m-aminobenzalde(muted W131 Petroleum ethal' ‘and Watef- Tha resulting
hyde ethylene glycol acetal; beta-(N-ethylanilino)ethylsolid was taken up in methylene chloride, the solution
trimethylammonium chloride; beta-(N-dodecylanilino) 25 was concentrated to a small volume, and anhydrous ether
ethyldimethylamine hydrochloride; beta-(Ncthyl-alpha-
was added. The crystalline material was collected and re
l1_aPhlhy1amin0)ethyltricthylammonium chloride; and the
crystallized three additional times. There was obtained
like.
0.9 g. of a black crystalline compound (IV) melting at
.
_ _
_
Representa?ve QH compounds contamins astwe
167° to 169° 0., having a molecular extinction coe?i~
methylene groups are acetoacetlc ester and its anndefs; 3° cient 24,600 at 562 my, and identi?ed as Q,2-dich1oro-4
the ester, nltrlle, amide, and mixed functions of_ malonlc
(pdimethylamino)_5_(p_to1uene sulfonyl) _cyclopentane_
sulfonyl n1tr1les;cyanoacetlc ester; cyanoacetamldes; beta-
3 91%_ cl 16 197
nitronitriles; beta-nitrocsters; malononitrile dimer; 3-(2- 35
1'6 52,7;
acid; acetylacetone; acetonedlcanboxyllc acid, its esters
and amidesicycllc l,3-d1k_etones; beta~ketonltrlle-s; betafuryl)acro1ein dimethylhydrazone; and the like.
1,3_dione_
Anatysm Calcd_ for CNHHO‘NSCIQ: C, 54.79%; H,
'
’
'
Found. C 54 79% _ H 4 12% . Cl
a‘
‘
’
'
’
'
'
’
’
'
There follow some examples which illustrate, but are
Examples 2.8
not intended to limit, the invention.
Example 1
40
Table III summarizes a series of experiments in which
c,_c__o__ol
5 g. of ‘the coupler shown in column 2 is dissolved in
é
+NaO:S-—CeH|—CHa(D) + OIHIN(CH1)B -——-»
472 g. of N,N—dimethylformamide and heated in turn
0: \ / =0
with 5 g. of QH compound (column 3) and 5 g. of com
0
pound MY (column 4). The mixture is then warmed on
(3( \(31
45 the steam bath for a few minutes, during which time the
(I)
(m
(m)
Ex.
Coupler
QH
(colorformer)
compound shown in column 5 is formed.
TABLE III
MY
Product
A--C=C—Z
Q—0=C|—Y
I X!
2 ____ .. Cl—O==G--Ol
1 XI
A1
C I
(F: )I ((51%):
1
D-(OHI)INCBHA—C=C—ON'
OFl
l
F:
A
C
Fl
A
C
F:
Cl = 01
P'(CH:)lNCnHA-C=C—CN'
Red (550:300).
F:
01 =tlzol
A
DI
p-(cH.),NC.H.-C=0—S0,0,H.CH,(p)
F;
0 .... .. Cl—C=O-Cl
F;
Red (503:370).
F:
F:
6 ____ ._ C1—C==O—Ol
F:
C]
IJ—(OHI):NCQH4—C=C—CN-
Fl
4 ____ __ Cl—C=C-—Cl
Orange-red (530).
(Fae): (‘Fl’)!
l
3 ____ __ C1-C=C—-Cl
Color (A man-mp)
F:
B1
0
lD-(CH|)INCnH4]:=C=C—H
Fl
Yellow (~).
Fl
Pale green (--)t
=C~CN
Fl 21F:
7 .... .. CI—O====C-—Cl
F1
Fl
CF:
See footnote at end or table.
A
C
p-(OHa)|NC|H|—C=C—-CN
F:
/
(ilFs
CF:
Red ('-);
3,093, 677
9,
El.
Coupler
(oqogr-
10
MY
Product
Color (A man-mp)
tor-mar)
A—C=C--Z
I.
l 1*(3
8--.--- Gl-—C==C-—Ol
01:
Q-O=C-—Y
a
A
0=0
C
p-(CHi):NCiH.~C=C—0N
Ch-
001:
Red (-J.
=0
C
él;
1m Table III, A, standirm alone, represents N ,N-dimethyianillne; B, 1,1-b1s(p-dimethylaminopheny!)ethylene; Q sodium
cyanide; and D, sodium p-methylphenylsul?nate.
Examples 9-26
Table IV summarizes a series of experiments in which
0.0005 mole of the coupler and 0.0005 mole of the QH
compound were dissolved in 3-4 g. of N,N-dimethylform
amide. To this solution there was then added 0.0005 mole
See tootnote at end of table.
of MY compound. The reaction mixture was stirred at
room temperature for several minutes. During this time
the reaction mixture developed the color shown in coiumn
5. Slight warming in a bath at 40-50‘ C. increased the
rate of color formation in those instances where it was
slow in developing at room temperature.
3,093,677
I In Table IV, A, standing alone, represents N,N-dimet,hylaniline; B, 1,l-bls(p-dimethylaminophony!)eth lene; D, sodium -meth l hen l l?n
E, sodium methylsul?nate; F, sodium butylsul?nate; G, sodium nitrite; and H, sodium benzylsul?nate.
y
p
yp
y su ate
Q being as defined above. B represents all of the mole
Table V presents a list of additional aromatic QH com
cule except Q, i.e.,
pounds containing electron-attracting groups which may
be substituted for the N-dimethylaniline of Example I,
in the process of Example I, to give the compounds shown
in the second columns. Table VI sets forth the same
information for some representative active methylenic
compounds. ‘In these two tables the generic formula of
the product molecule may be written
Q—C"'—0-50a—UuHr-0H:(D)
o=$
=0
75
3,093,677
'
TABLE V
Example
QH (color-ionizer)
Product
27 _________ .,
N-methyl-N?-cyauo-ethylan?ine ......................... -_
,
HJC
\\I—C¢H¢—B
NC-CHrC :
28 ......... ._ Furylacroleinphenylhydmmna ___________________________ ._ 0sH:-NH—N=CH—CH=0Hl0/“—B
29 ......... ._ Pynole-Z-aldehyde dimethylhydrazona____________________ -. (CHx)r—N-N=CHlNJ'>~B
30 ......... .. 1-benzoyl-2-pheny1hydrazine __________ .7 __________________ _.
‘1
C?s-é-IITH
N-B
JJsHs
I IB
31 _________ __ 1,2,5-trimethy1pyrrole_ .................................... __ Etc-LN1:013:
éHl
SOaNa
32......... -- Bodiumsalt oI1-naphthol-2-su1ionieaeid __________________ __ HO®B
33 ......... -. p-Methoxybenzaldehyde-p-methoxyanil, __________________ __ H:0—~0—-C¢H;—N—€J—B
H|CO—CuH4—I‘£'
34 _________ _,
N-n-butylcarbazole ________________________________________ _.
B
N
(54H.
35 _________ _-
m-Diethylaminophenol ___________________________________ __
(CaHahN
B
H
'
35 _________ _-
?-(N-ethylanilinoethyl)trimethylammonium chloride ______ __
9
G9
Cl(CH|):N-CH1CH:—N
V
43:11:
37 ......... __ Benzaldehydebhenyihydrazoné ........................... _- ©CH=NNH©~B
38 ......... .. 1.l-bis(pdhnethylaminophenybethylene .................. _. [(CH:):N©—]C=CH—B
I
39 _________ __ l-phenyI-S-methylpyrazolone ______________________________ __
CoH5—1I1'—-—C=O
N\
\ / —-B
G
éH.
CH;
40......... -- 2,6—dimethyInh-M1
HO©—B
H:
41 ......... __ Resorcinol dimethyl ether _________________________________ __ emu-Q43
7
42 ......... _. Indole........ -.
6H;
(F4;
N
H
B
3,093,677
15
perhalocarbyl radicals of up to 12 carbons and, jointly,
from the group consisting of divalent perhalocarbyl and
TABLE VI
oxoperhalocarbyl radicals of up to 6 carbons, any oxo
carbonyl oxygen being carried by a carbon joined to one
Er
QH (color-former)
Product
43- .
Malononitrile dimer _____ _.
(CN)aC=C(NH|)CCH(CN)—B
44..-
Ethyl acetoacetate ______ ..
CHuCO——CH—B
cyano, nitro, carboxy, carbamyl, halocarbonyl, and alkyl
sulfonyl, alkarylsulfonyl, arylsulfonyl, aralkylsulfonyl,
0002115
45... Acetylacatone ___________ ..
(CHaCOhOH-B
46-..
Malononitrile ___________ ._
(CNhCH-B
47-..
Ethylcyanoacetate ______ ..
(CaHrOCO)CH-—B
of the depicted doubly bonded carbons; Y is an electro
negative radical selected from the group consisting of
5
pound QH selected from the group consisting of aromatic
compounds containing an electron-donating group other
than methoxy and compounds containing an active
methylene group.
N
48- .
Acetoacetaullide ________ ..
alkoxycarbonyl and alkylcarbony of up to 12 carbon
atoms; and Q is the monovalent organic radical of a com
10
CHaCOCH-B
15
CONHCgH;
49.--
Diethyl malouate ....... ._
2. The process of producing a compound of claim 2
which comprises reacting, at a temperature between about
—10" and 100° C.: (1) a compound of the formula
(CiHrO0C)gCH-—B
(CzHsO C O)
50.--
Ethyl malouamate ______ ._
CH-B
20
(HaNCO)
(COOCzHa)
51-.. Dlethyl acetonedlcarbox-
ylste.
CH-B
CaHaOOCCHaCO
25
O
l
52.--
1,3-eyclohexanedione ____ ._
wherein: A is halogen of atomic number 9—3S; X1 and
X2 are selected individually from the group consisting of
B
30
O
53-..
2 - ethoxycarbonylcyclo-
c O 0 023‘
B
O
54-..
Aeetoaeetonitrile ________ ..
55... Methylsulfonylaceto-
(OHaCO) (ON) 011-13
(OH;B0:)(GN)CH—B
nitrile.
56.--
Cyanoaeetanilide ........ _.
(CONHCrH5)(CN)CH-—B
57...
Ethyl
(COOCzHa)(NOa)CH—B
58.-.
Nltroacetonitrile ........ ..
nltroacetate ..... ..
of up to 12 carbons and, jointly, from the group con
sisting of divalent perhalocarbyl and oxoperhalocarbyl
——
pentanone.
monovalent perhalocarb'yl and oxoperhalocarbyl radicals
radicals of up to 6 carbons, any oxocarbonyl oxygen being
carried by a carbon joined to one of the depicted doubly
35 bonded carbons; and Y is an electronegative radical se
lected from the group consisting of cyano, nitro, car
boxy, carbamyl, halocarbonyl, and alkylcarbonyl of up
to 12 carbon atoms; and (2) an organic compound QH
selected from the group consisting of aromatic compounds
4O containing an electron-donating group other than methoxy
and compounds containing an active methylene group.
3. The process of claim 2 accomplished in an inert
reaction medium.
(ON) (NOr)CH—B
4. The process which comprises reacting, at a tem
45 perature between about —l0 and 100° C., tetrachlorocy
clopentene-l,3-dione, N,N-dimethylaniline, and an alkali
metal sul?nate.
S. The process which comprises reacting, at a tempera
ture between about -—l0 and 100° C., l,2-dichloro-l,2-bis
The compounds of this invention are colored and are
useful as dyestuffs in all applications where dyestuffs are
known to be useful, such as coloring pigments for plastics,
(w-chloroper?uoroethyl)ethylene, N,N - dimethylaniline,
paints, and the like. They are also useful in the dyeing 50 and a metal cyanide.
of textiles as shown below:
6. The process which comprises reacting, at a tempera
A dye bath is prepared using 10,000 g. of water con
ture between about ~10 and 100° C., l,2-dichloro-1,2-bis
taining 2 g. of a sulfonated lignin dispersant (“Mara
(tri?uoromethyl)ethylene, N,N-dimethylaniline, and a
sperse CB,” Marathon Co.) and S g. of acetic acid. A 55 metal cyanide.
solution of 2 g. of 2,2-dichloro-4-(p-dimethylamino
7. The process which comprises reacting, at a tempera
phenyl ) -5- (p-toluenesulfonyl) cyclopentene- l ,3 -dione, pre
ture between about ~10 and 100° C., l,2-dichloro-l,2-bis~
pared as in Example I, in 100 g. of acetone is added with
(tri?uoromethyl)ethylene, N,N-dimethylaniline, and an
stirring. The dye bath is heated at 80—95'’ C. and
alkali metal p-toluenesul?nate.
1
swatches of cellulose acetate, nylon, silk, and wool weigh
8. The process which comprises reacting, at a tempera
ing 10 g. each are added. After a few ‘minutes the cellu 60 ture between about -—10 and 100° C., l,2-dichloro-l,2-bis
lose acetate fabric is dyed yellow and the nylon, silk, and
( tri?uoromethyl ) ethylene, l, 1 -bis (p-dimethylaminophen
wool are dyed brown. These dyeings have good light
yl)ethylene, and a metal cyanide.
and wash-resistance.
9. The compound having the formula
Since obvious modi?cations and equivalents in the in
vention will be evident to those skilled in the chemical
arts, I propose to be bound solely by the appended claims.
I claim:
1. A compound of the formula
70
wherein: X1 and X2 are selected individually from the
group consisting of monovalent perhalocarbyl and 0x0 75
3,098,677
17
18
10. The compound having the formula
12. The compound having the formula
D'(GH:)|N—CaH4—C=O~GN
p-(OHa)nN—0eTI¢—-C‘_C—0N
C F;
( F1): ( F2):
1
x
5
11. The compound having the formula
F,
61 $1
13. The compound having the formula
p_(o Ha) 2N_C?HI_O=C_CN
F,
C F!
0:0
D-(CHx):N—~C‘H4—C=C—SO|—CnH¢-—C H;
10
F‘
F’
No references cited.
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