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Heterocycles as Structural Units in New Optical Brighteners.

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Heterocycles as Structural Units in New Optical Brighteners
By Alfons Dorlars, Carl-Wolfgang Schellhammer, and Joseph Schroeder['I
Dedicated to Professor Siegjiried Petersen on the occasion of his 65th birthday
Optical brighteners are used in detergents, textiles, paper, plastics, and paints. Most optical
brighteners contain heterocycles such as coumarins, 2-pyrazolines, naphthalimides, pyrazoles,
triazoles, oxadiazoles, and triazines. In this article the syntheses, properties, and applications
of new optical brighteners are described with references to patent literature.
1. Introduction
Optical brighteners are colorless fluorescent dyestuffs that
absorb in the near ultraviolet (3500-3900A) and fluoresce
in the violet to blue region of the spectrum (4250-4450A).
Thus, by their use the reflection deficit of yellowish substrates
can be compensated and even overcompensated. The first
review of organic fluorescent dyes and their industrial use
in this Journal appeared 26 years ago['I, and since then new
substrates that require brightening have come into use; the
increased demands on fastness to light and to other agents
in use have, however, been satisfied by research in the laboratories of the dyestuffs industry, and the results are recorded
in patent applications. Reference should also be made to
some reviews of the whole
Except for some linearly extended, conjugated carbocyclic
systems such as derivatives of distyrylbenzene and 4,4'-distyrylbiphenyl, the optical brighteners that are used industrially
contain heterocycles. The heterocycle may play either of two
roles: the basic skeleton of the brightener may be a heterocycle,
for example in coumarin derivatives or 2-pyrazoline derivatives, or alternatively, the fluorescence of a conjugated system
may be increased and shifted bathochromically. We can thus
distinguish between heterocycles themselvescapable of fluorescence and heterocycles attached to conjugated systems that
can fluoresce. Admittedly there is an overlap in many cases,
but nevertheless we shall use this classification in the present
attempt to review, from the patent literature, the heterocycles
used as structural units in the new optical brighteners.
2. Synthesis of Heterocyclic Systems Themselves Cap
able of Fluorescence
2.1. Synthesis of Coumarins and 2-Quinolones
One of the oldest optical brighteners based on coumarin
is 7-(diethylamino)-4-methylcoumarin( f ), which is prepared
by the Pechmann coumarin synthesis from m-(diethylamino)phenol and ethyl acetoacetate.
&
.a,-
Numerous variants of compounds (1) that carry hydrogen
or a methanesulfonyl or butanesulfonyl group in place of
the N-ethyl group are also useful brightener~'~!Work on
compounds of type ( 1 ) has utilized the observation that coumarin derivatives fluoresce strongly when an electron-donor
substituent is present in position 7c4! Coumarins also fluoresce
strongly if C-5 and C-6 are annelated to benzo rings as in
( L ? ~ ) - ( L ? C ) ~ ~ ~or
, if a 2-thienyl (3)I6l or 2-benzoxazolyl group
(4)"' is present in position 3. The fluorescence of 3,4-, 6,7-,
and 7,8-benzo-annelated coumarins is much weaker than
that of compounds of type (2).
More powerful brightening effects or better light fastness
is obtained with derivatives of 3-phenyl- or 3-heterocyclyl-coumarins. These compounds also must have electrondonor substituents if they are to fluoresce optimally; this condition
is satisfied by alkoxy, alkylthio[121,or acylamino groups or
heteroaryl containing an excess of n-electrons; these may be
in the p-position of the 3-phenyl ring or in the 7-position
of the coumarin.
7-Alkoxy-3-phenylcoumarins(6) are prepared by the Perkin-Oglialoro synthesis[' 31 from resorcylaldehyde ( 5 ) and
sodium phenylacetate with subsequent hydrolysis of the intermediate product by alkylation of the hydroxyl
HO
a;p.H2yQ
(5)
c H3
R2N QH
+
R2N
R-0
R = C,H,
0
Angew. Chem. internai. Edit.
1 Vol. 14 ( 1 9 7 5 ) 1 No. 10
&+&
'
0
HsC-0
'
0 0
(61
(1)
[*] Dr. A. Dorlars, Dr. C.-W. Schellhammer, and Dr. J. Schroeder
Bayer AG, Wissenschaftliche Laboratorien
509 Leverkusen (Germany)
0
H, C-C0-0
COONa
Substituted phenylacetic
or 4,4'-biphenyldiacetic
acid['61may replace the phenylacetic acid. 7-AlkoxyJ-heterocyciylcoumarins such as (7) are obtained from 4-alkoxysalicylaldehydes and the corresponding substituted acetic acids[' 'I.
665
Precursors of (14), namely 7-nitroand 7-(acetylamino)-3-phenylcoumarin (22) can be prepared by PerkinOglialoro synthesis.
3-(p-Aminophenyl)cournarin ( 2 0) is prepared by Knoevenagel condensation" 81 of salicylaldehyde with p-nitrobenzyl
cyanide, giving the iminocoumarin (8), followed by hydrolysis
to (9) and catalytic reduction[*9].
(S), X
(9).
x
(Zl), R = NO,
R
(22). R = NH-CO-CH,
Since 4-nitro- and 4-(acetylamino)salicylaldehyde are not
readily available industrially, 4-(acetylamino)salicylideneaniline[25]can be used as the aldehyde component. This variant
of the synthesis affords 7-(acetylamino)coumarin derivatives
(23)IZ6] and is particularly suitable for the preparation of
coumarins carrying heterocyclic groups attached in the
nitrogen in position 3.
= NH
= 0
7-Amino-3-phenylcoumarin (24) can be obtained by successive Knoevenagel condensation of the substituted benzaldehyde ( 1 2 ) with benzyl cyanide, giving the acrylonitrile derivative (22), cyclizing ether fission by aluminum chloride in
benzene to give (23), and acid hydrolysis[20!
(1.21
(13). X
(14). X
= NH, R = NH-CO-CH,
=
0,R = NH,
(14) is also accessible by processes that resemble the Pechmann coumarin
Thus, it is obtained when ethyl
3-hydroxy-2-phenylacrylate(24) is added slowly to m-aminophenol in boiling 1,2-di~hlorobenzene~~*~
or in nitrobenzene
containing aluminum chloride[29!
The synthesis of (24) can be simplified by adding benzyl
cyanide to an alkaline solution of 4-amino-2-methoxybenzaldehyde (15) as obtained on treatment of 2-methoxy-4-nitrotoluene with sodium disuifide in aqueous-alcoholic alkalif2 ;
the acrylonitrile derivative ( 2 6 ) is isolated and is cyclized
by aluminum chloride in benzene to (27)[221, whence ( 1 4 )
is finally obtained by acid hydrolysis.
(17)
If the synthesis Of f Z 4 ) is started from the sulfamidic ester
(28), the aldehyde (29) is obtained on treatment with sodium
disulfide, and with benzyl cyanide this gives (20); heating
of ( 2 0 ) with 50% sulfuric acid then affords ( 2 4 ) t Z 3 ] .
When the acrylic ester derivative ( 2 5 ) is heated with marninophenol to 165 "C, (24) is obtained without the addition
of a
Thecoumarin derivatives (10) and (14) are merely intermediates; they become optical brighteners only on acylation
of the amino group or on incorporation into heteroaromatic
having an
of n-electrons (see Section 3.9).
7-(Diethylamino)-4-methy1-2-quinolone
( 2 6 ) which is structurally similar to 2, also
strongly[4, 311.
CH3
-
HzNQCH-FQ
R = SOz-N(CH,),
0-R
CN
(20)
666
(14)
The industrially useful properties of 2-quinolone derivatives
are also improved by the presence of a phenyl group in position
3. 7-Amino-l-rnethyl-3-phenyl-2-quinolone
( 2 8 ) can be preA n g e r . Chem. inrernat. Edit.
J Vol. 14 ( 1 9 7 5 ) 1 No. I 0
pared by condensing 2-(methylamino)-4-nitrotoluene with
ethyl phenylglyoxalate and reducing the intermediate product
( 2 7 ) or by treating the phenylacetamide ( 2 9 ) with sodium
disulfide in an alkaline-alcoholic medium[331.
C H3
C H3
(27). R ' = NO,
(28). R ' = NH,
The fluorescence maxima of 7-amino-3-phenyl-2quinolone
derivatives are shifted hypsochromically from those of the
corresponding coumarinderivatives; for this reason 7-(dimethylamino)-1 -ethyl-3-phenyl-2-quinolone,
which is prepared by
methylating the 7-amino compound with formaldehyde/hydrogen, is an optical brightener'341,whereas 7-(dimethylamino)3-phenylcoumarin is too highly colored.
The upper portion of Table 1 shows the variations in substituents introduced into the 1-phenyl ring; the lower portion
lists the industrially important 2-pyrazoline derivatives.
1,3-Diphenyl-2-pyrazoline-5-carboxylicacid derivatives
(33) and pyrazoline derivatives ( 3 4 ) disubstituted in positions
4 and 5 are occasionally synthesized by 1,3-dipolar addition.
C 1~
~
c1~
~
S
O
1
H
s
o
- H3) 2N + HzC
( =CH-COOCzH,
C
~
z
-
N
H( 3 ) 2
-
c
C OOC
(33) [531
2.2. Syntheses of ZPyrazolines
The industrially useful brighteners in this class of compounds are derived from 1,3diphenyl-2-pyrazoline,which is
a fluorescing system in its own right. Some authors describe
this grouping as a chromophore:
C
l
w
e
C
N
V
( 3 4 )I541
The 2pz electrons of the N-I atom are then considered to
interact with the n-electrons of the C=N
Other
workers believe that the strong interaction of 1,3-diphenyl-2pyraz~line[~']
with light is better described by assuming intramolecular charge transfer (ICT)[36J
in the directions indicated
by the arrows in the formula. There have been studies of
the influence of structure, solvent, and temperature on this
Industrial syntheses of 1,3-dipheny1-2-pyrazolines,e.g. (30)
and (31) employ phenyl vinyl or P-chloroethyl phenyl ketone,
or alternatively Mannich bases from acetophenoneand formaldehyde with secondary amines and substituted phenylhydrazines, as the starting materials.
Table 1. 3-(p-Chlorophenyl)-l-phenyl-2-pyrazolinessubstituted in the 1phenyl ring(Ae =anion). Top: Illustrationsofthe variants. Below: Industrially
important brighteners.
C
R
1
W
h
O
R
Ref.
COO-CH,-CH=CH,
COO-CH,-COO-C,H
1421
1431
5
SO ,+CH ,).--SO,H
SOz-0CH,
148. 391
1491
A
H ~ N - N H~ S O ~ - ( C I I ~ ) Z - +O C1
H
1501
Sop-NWN-R
,
SO - ~ C H,),-COO+CH
,),-~%cH
,),
~e
1511
1571
1391
1581
~401
1,3-Diphenyl-2-pyrazolinescontaining functional groups
are synthesized from substituted phenylhydrazines or by
changes effected on the preformed pyrazoline. Thus, (32)
S O ~ ~ ( C H , ) ~ - O - C H ~ C H , ) - C H ~ - ~ H ~ C H CP
,)~
SO,-CH,
SOz--C4H9(n)
can be obtained via the two routes shown.
[a] Further substituents: 2-methyl and 5-chlorine in the 3-phenyl ring.
Angew. Chrm. infernat. Edit.
1 Vot. 14 ( 1 9 7 5 ) 1 No. 10
1591
1411
Em1
667
1,3-diphenyl-2-pyrazolineswhose fluorescence
has a red tint with the 1,5diphenyl-3-styryl-2-pyrazolines( 3 5 )
that can be obtained from dibenzylideneacetone and relevant
phenylhydrazines permits any desired hue of white to be introduced.
R
(43)
H
I
-
X
(44)
NH2
NO2
(45)
NH2
(46)
(47)
X = S 0 3 H , NOz, C1
2.3. Syntheses of Naphthalimides
Naphthalimides with electrondonor substituents on C-4
and C-5 fluoresce strongly. Whereas the 4-acetylamino derivatives ( 3 6 ) to ( 3 8 ) whiten to a green tint, the alkoxy derivatives
such as (39) and (40) produce neutral white shades on synthetic materials (Table 2).
serves for the production of the brighteners (36)-(38) can
also be synthesized from ( 4 5 ) by way of the amine (46)1861.
4,5-Dichloronaphthalic anhydride (49), the intermediate
for brighteners of type (40)[871,is obtained by oxidizing 5,6dichloroacenaphthene (48)[881or by treating 1,4,5,8-naphthalenetetracarboxylic acid (50) with sodium hypochl~rite[~~].
Table 2. Naphthalimide-type brighteners.
c1 c1
(48)
c1
c1
Hood
149)
COOH
(50)
2.4. Synthesis of Other Fluorescing Heterocyclic Systems
(36)
(37)
(38)
(39)
(40)
R'
R2
R3
Ref.
Alkyl
Alkyl
H, Alkyl
Alkyi
AIkyl
NH-COXH3
NH-CO-NH-C,HS
N(CH,)-COXH,
OCHJ
OC2Hs
H
H
H
H
OCZHS
[621
1621
r631
1641
"W
Numerous variants of the naphthalimide whitening agents
of types ( 3 9 ) and (40) are known and make it possible
to meet the requirements of industrial application more adeq ~ a t e l y '6~6 -~731.
. In order that 4-methoxynaphthalimide derivatives can also be used for acid-modified polyacrylonitrile
fibers numerous variants have been prepared, containing
basic and, in particular, quaternary ammonium groups[74The starting material for industrial syntheses of naphthalimide derivatives is acenaphthene that has been sulfonated,
nitrated, or chlorinated in position. 7 [thus giving ( 4 1 ) ] and
then oxidized to the naphthalic acids ( 4 2 ) by dichromate[821.
On drying, these acids are converted into their anhydrides
(43).
Among the heterocycleswith one heteroatom the derivatives
of benzofuran acting as optical brighteners occupy much space
in the patent literature. 2-Phenylbenzofuranis formally a transfvted ~ t i l b e n e ' ~the
~ ] ; 2-phenyl group may be replaced by
styryl, stilbenyl, or benzazolyl groups. p-(2-Benzofurylvinyl)benzonitrile ( 5 1 ) is formed on condensation of 2-benzofurancarbaldehyde with dimethyl 4-cyanobenzylphosphonate in the
presence of an alkali metal alk~xide[~l!
m
C
H
0
+
''
0-
(H,CO)~PO-CHZ
m
CN
H
-
C
-----)r
H
O
C
N
(51)
Benzodifurans can also be useful brighteners, an example
being (52)[921which is formed in a redox reaction of methyl
pphenylbenzoylacetate with p-benzoquinone.
C OOC H3
Utilizable fluorescence is also shown by derivatives of benzothiophene e. g. 5-methyl-2-phenylbenzothiophene
S,S-dioxide (53)[93! Chlorite-resistant brighteners can be derived,
in particular, from dibenzothiophene S,S-di~xide['~J.
4-Chloronaphthalic anhydride (43), X = C1, is also formed
on chlorination of naphthalic acid at pH 7.3[82J,and mild
treatment with ammonia or aliphatic amines gives the imides
(44)[831.
The sulfonic acid group or halogen atom of (44) can be
all
replaced by an amino, hydrazino, or hydroxyl
three substituents X in ( 4 4 ) can be caused to react with
sodium methoxide to afford (39)IB5].The amine (47) that
668
- H3C
(53)
\
od 0
'
Angew. Chem. internar. Edit.
Vol. 14 ( 1 9 7 5 ) / No. 10
Among the fluorescing nitrogenous heterocycles the benzodipyrrole (54) is especially readily accessible-from m-phenylenediamine and benzoin[y5!
H
H
Fluorescence is also, surprisingly, shown by 2-(2,5-dimethoxypheny1)-I-pyrroline (55), which can be synthesized by
condensing 4-aminobutyric acid with hydroquinone dimethyl
ether in polyphosphoric acidfy61.
H3C0'QOcH3+
H2N-(CHz),-COOH
-
H3C0@
OC H3
HOOCI: HC 14C Hz) 2-C HC 1-C OOH
(61)
J.
tance attaches to the synthesis of (63) which starts from
2,5dichloroadipic acid (61) and proceeds by way of the tetrahydro-2,5-thiophenedicarboxylic
acid (62)1'02].
3. Syntheses of Heterocycles Attached to Fluorescing
Conjugated System
3.1. Conjugated Systems Containing 1-Pyrazdyl or ZIndazolyl
Groups
(55)
Optical brigtheners are also found among the derivatives
of pyrazine, an example being the diaminopyrazinedicarboxylic acid derivative (56)I9'].
C H3
CH3
CH3
CH3
+
H3C-NH
H3C-NH-CO
Whereas nowadays pyrroles do not play any part as substituents of fluorescing conjugated systems, the I-pyrazolyl group
is a constituent of some important optical brighteners. I-Pyrazolyl derivatives are obtained by treating P-dicarbonyl compounds with the relevant substituted hydrazines. For example,
the 5-methyl-I-pyrazolyl derivative (65) is obtained by reaction of acetoacetaldehyde with 7-hydrazino-3-phenylcoumarin
( M ) , which is itself obtained by diazotization of ( 1 4 ) and
subsequent reduction by sulfite[103!
H3C-C O X H2-C HO
1
N,X N H q H 3 f l N H 2
N
CO-NH
CH3
Pyrazoloquinolines such as ( 5 8 ) , which can be used as
whitening agents, are formed when pyrazoles such as (57)
are heated with phosphorus oxychloride[y8!
COOH
CH3
Some brighteners are also found among the derivatives
of 2,5-furandicarboxylic acid (60) and of 2,5-thiophenedicarboxylic acid (63). Compound (60) can be prepared in 50 %
yield from tetrahydroxyadipic acid (e. g. mucic acid or a sugar
acid) by treatment with concentrated
or from methyl
2-furancarboxylate (59)" Ool via several steps.
(591
(60) and (63) are also formed on carboxylation of the
potassium salts of the corresponding monocarboxylic acids
(in the presence of CdF, at 320"C/50atm)~10'! More imporAngew. Chem. internat. Edit.
Vol. 14 (1975) 1 No. 10
(65)
Since, however, compounds containing a 5-substituted 1pyrazolyl group have less advantageous properties than the
3-substituted analogs, special techniques must be applied to
provide the compounds containing 3-substituted 1-pyrazolyl
groups. If the aldehyde is replaced by its dimethyl acetal
and the mineral acid used for cleavage of the acetal grouping
is added only after the formation of the ketone hydrazone
(66), then the 3-methyl-I-pyrazolyl derivative (67) is
obtained ' 3!
Analogous reactions are undergone by 7-hydrazinocoumarins containing heterocycles such as 1,2,4-triazole or 4chloropyrazole in position 3 ['04], or N-alkyl-4-hydrazinonaphthalimide~['~~!
In place of oxoaldehyde acetals, alkyl or aryl
3-chlorovinyl ketones may also be used. To synthesize the
3-substituted 1-pyrazolyl derivative from 2-methoxyvinyl
phenyl ketone (68), the hydrazine used is first acylated in
the P-position and thus the desired compound (70) is obtained
by way of the intermediate (69)" 06!
669
3.2 Conjugated Systems Containing SPyrazolyl Groups
S03H
S03H
+ 2 H,C-O-CH=CH-CO-R
By coupling diazotized 4,4'-diamino-2,2'-stilbenedisulfonic
acid i..fl;i\ ic acid) with 1-phenyl-Zpyrazoline one obtains
compound (79), whence (80) results on dehydrogenation'"''.
(68)
(69)
R-CO-CH=CH
R
S03H
CH=CH-CO-R
CsH5
Pyrazoles disubstituted in positions 3 and 4, e.g. (72),
can be prepared by Vilsmeier formylation of ketone hydrazones such as (71)[1011. (67) can be chlorinated by sulfuryl
chloride in tetrachloroethane, yielding (73)[Io81, or it can
be converted into (74) by means of formaldehyde/toluenesulfonic
7-(2-Indazolyl)coumarinssuitable as optical brighteners are
accessible by conversion of (14) into (75) by reaction with
o-nitrobenzaldehyde and subsequent cyclization to yield (76)
by heating with triethyl phosphite; or ( 1 4 ) may be condensed
with, e. g. 2-azido-l-naphthaldehyde,
yielding (77), from which
nitrogen can be removed thermally with the production of
(78)['Io1.
3.3. Conjugated Systems Containing
Groups[ ' la]
1,fSTriazol-1-yl
The known synthesis of 1,2,3-triazol-l-y1 compounds by
the addition of azides to alkines has been mastered also by
industry, so that we meet such compounds among stilbene
as well as among coumarin derivatives. The intermediate (83)
needed for the manufacture of the bis(triazoly1) brightener
( 8 4 ) is obtained from the 4-amino4-nitro-2,2'-stilbenedisulfonic acid (81) that is readily available industrially by diazotization and coupling with toluenesulfonamide; the azide (82)
then obtained with loss of toluenesulfinic acid[112a1
can be
converted into (83) by acetylene under slight pressure" l2].
The compound (86) is obtained similarly from 7-azido-34~to1yl)coumarin (85) by the addition of acetylene, and with
dimethyl sulfate it gives the quaternary derivative (87)['131.
3.4. Conjugated Systems Containing 1,Z,STriazol-Z-yl~roups
The great stability of the 1,2,3-triazol-2-y1 group bonded
by its central N atom has long been known from the chemistry
of dyes for the cases of annelated triazolyl groups and in
particular of benzo- and naphtho[ 1,2-d]triazoles. Attempts
to achieve stability to hypochlorite bleaching solutions and
improved light fastness by incorporating the N-atoms of flavic
acid into the heteroaromatic system of the naphthotriazole
have proved successful. The first representative of this class
of compounds, (88), is prepared by coupling diazotized flavic
670
Anyen'. Chrm. internar. Edir.
Vol. 14 ( 1 9 7 5 )
1 No. 10
acid with 2-naphthylamine-5-sulfonic acid and oxidation of
the resulting o-aminoazo dye with hypochlorite or copper(1r)
salts" 141.
Table 3. Brighteners containing 1,2.3-triazol-2-yl groups.
'S03H
SO,H
(88 I
S0,H
The marked greenish tint of (88) can be shifted in the
direction of neutral white by dispensing with one of the naphthotriazole groups, although this is at the cost of efficiency.
The compound ( 8 9 ) is stable to hypochlorite bleaching liquors
and peroxides; it is suitable for whitening cellulose and polyamide from washing baths['l5I.
The cyano compound ( 9 0 ) is used as polyester brightener['l6].(89) and (90) are prepared analogously to (88)[L16a1.
The patent literature contains numerous variants of the compound types (88)-(90)r"6b1, e. g. (84). Moreover, the
benzobis(triazo1e)stilbene compounds (91) have been developed as polyester brighteners" ''I.
These compounds (91 ) are prepared by coupling 5-amino-2(p-toly1)-benzotriazolewith diazotized p-toluidine or with the
diazo component corresponding to the group R, and are
then cyclized, e. g. to ( 9 2 ) . The methyl groups can be condensed
with benzylideneaniline in dimethylformamide in the presence
of strong bases (KOH), yielding the distilbenyl compound
("anil synthesis")" 81.
SOsH
R'
R'
Ref.
While ( 9 6 ) confers white tints on cotton and polyamides
with good
derivatives without the carboxamide
group, e.g. (97), give clear neutral white shades that are
light-fast and resistant to hypochlorite bleach liquors['231.
The tetrasulfonic acid (98) produced by subsequent sulfonation of ( 9 7 ) is equally stable and is so far the only water-soluble
stilbene brightener that can be used in a reactant resin form
without the necessity of wasteful after-washing. Compounds
(99), (loo), and (101) are good brighteners for polyamides.
Sulfonamides derived from disulfonic acids of type ( 9 7 ) are
suitable for brightening polyester materials to be spun['26a1.
Synthesis of the 1,2,3-triazol-2-yl derivatives (96)-( 100)
is best achieved by Pechmann ~ y c l i z a t i o n [ ~
of*ct-hydroxy~~
imino hydrazones (102), which in turn can be provided by
coupling diazotized arylamines-here especially flavic acidwith reactive methylene compounds, e. g. nitroacetaldoxime
(R'=N0,,R2=H)[1Z2*I**], or by condensing aromatic hydrazines, here 4,4'-dihydrazino-2,2'-stilbenedisulfonic
acid, with
the readily available a-hydroxyimino ketones (R =C,H 5 ,
R2=H, etc.)[1291.
/ 1 0 2 ) , X = OH
R'
1
A r-N/N
I
(1031, X
R2
H
0-Acyl
/I04), X = H
X
In the coumarin series too this procedure leads to effective
brighteners. The naphtho[l,2-d]triazole compounds (93)" 19]
and (94)[1201obtainable from the amines (10) and ( 1 4 ) ,
respectively, are polyester brighteners, while the compound
( 9 5 ) accessible from diazotized ( 1 4 ) and 3-butoxy-p-toluidine
brightens PVC well['"!
The monocyclic 1,2,3-triazol-2-yl group is very stable and
capable of varied substitution and it brings new possibilities
into the chemistry and technology of optical brighteners. This
can be illustrated by some examples from the stilbene series
(Table 3).
Angew. Chem. inrernar. Edir. / Vol. 14 ( 1 9 7 5 ) / No. I 0
Four configurations can. in general. be considered for r-hydroxyimino hydrazones such as (102) : syn- and anti-hydrazones can take part in triazole ring closure, especially the syn-hydrazone anti-oxime. For this synthesis the hydroxyimino group
is acylated, giving ( I O S ) , e. g. by acetic anhydride, urea" 301,
R'
N
0
A~-NH-N=CR'
+
R~-CN
Ar-NH-N-C-R'
I
CN
671
or isocyanates" I ] ; after nucleofugal departure of the acyloxy
anion an intermediate (105) is obtained, which can stabilize
itself in several ways, in which a part is played by the possible
removal of the N-proton that is capable of hydrogen-bridge
formation.
The products may be not only the desired triazoles by
reaction (a) but also, from anti-hydrazones and/or aromatic
R2, the acylhydrazines by reaction (b) (Beckmann cleavage),
or, further, by reaction (c) when R Z= H, the hydrazonoglyoxylonitriles and subsequent products therefrom. For high yields
of triazole the reaction conditions must thus be carefully
optimized in each individual case.
The compound (101) is advantageously obtained by oxidative cyclization of the coupling product of diazotized flavic
acid with 0-aminocinnamic ester (104), R I =C,H5,
R2=COOC2H5[126!In some cases higher yields of triazole
are obtained more easily if the hydroxyimino hydrazones
( 1 0 2 ) are first cyclized with dehydrogenation to triazole N I oxides (106)1'321,e. g. by copper(I1) salts, and these oxides
are then reduced to the triazoles (107).
1113)
In the coumarin series combination with 1,2,3-triazol-2-yl
groups leads to products that are particularly suitable as
polyester brighteners. A selection of characteristic examples
is given in Table 4.
Table 4. Brighteners of coumarin type containing 1.2.3-triazol-2-yl groups.
R'
Z
R2
Ref.
[a] H in place of CH,
Treatment of the reactive triazole N1-oxides (106) with
hydrogen chloride or phosphorus chlorides leads, when
R2=H, to chlorotriazoles (108)11331; reaction with acetic
anhydride leads analogously to acetoxytriazoles (109)[1341,
and, when R2=CH,, to acetoxymethyl derivatives (1
An example of an optical brightener of type ( 108) is compound
( 1 1l ) , which is obtained by condensation of 4-hydrazino-2stilbenecarbonitrile with cr-(hydroxyimino)benzylideneacetone, dehydrogenation of the hydroxyimino hydrazone to the
triazole N '-oxide and finally treatment with hydrogen chloride" 3 6 a 1
As examples of long-chain monotriazolylstilbenes may be
cited the cotton brightener ( I 12)[1361and the spun-polyester
brightener ( I 14). Whereas ( I 12) can be prepared, analogously
to (97), from 4-hydrazino-4'-phenyI-2-stilbenesulfonicacid,
( I 34)1136b3
is obtained from thedialdehyde ( I 13) by carbonyl
olefination[' 36c!
( 1 13) and numerous substituted derivatives thereof can
be prepared in good yields by Rosenmund reduction of dicarboxylic acid chlorides.
672
Compounds ( I 15)-(121) are prepared from 3-phenyior 3-heterocyclyl-7-hydrazinocoumarinsby condensation with
a-hydroxyimino-propiophenone, -benzylideneacetone, -pphenylpropiophenone or -diethy1 ketone, with subsequent cyclodehydration of the resultant hydroxyimino hydrazones.
N a p h t h a b i d e derivatives carrying a monocyclic 1,2,3-triazol+
2-yl group in position 4 have also been described as polyester
brighteners. Since this class of compounds already fluoresces
at rather long wavelengths, bathochromic substituents should
not be introduced into the triazole nucleus. The best results
are obtained with (122a)['431or, even better, (122b)['441,
where R ' is ethyl or butyl in both cases.
The starting material for these compounds is N-ethyl- or
N-butyl&hydrazinonaphthalimide, which is condensed with
hydroxyiminoacetone to yield the a-hydroxyimino hydrazone
(102). For the preparation of (122a) the next step is dehydrogenation to the N-oxide (106), which then yields the halotriazoie (108) as described above. (122b) can also be obtained
in the usual way. However, if the readily accessible anti-acetoximino-acetone (123) is used as the starting material, (I22b)
H,-CO-O-N=CH-CO-CH,
(123)
is formed in 90% yield in a one-stage reaction['4481;but
it should be mentioned that this procedure cannot be applied
to hydroxyiminoaryl ketones.
Anyew. Chem. inremar. Edit.
1 Vol. 14 ( 1 9 7 5 ) / No. 10
3.5. Conjugated Systems Containing 1,2,3-Triazol4yl Groups
Since hydroxyimino ketones-especially hydroxyiminoacetone--can be readily arylated by diazo corn pound^^'^^^, fluorescing systems containing amino groups (Ar-NH,) can be
linked to a 1,2,3-triazolyl group attached through its atom
C-4, yielding compounds of type (124).
0
Ar-N2
Ao +
+
I
OH
Table 5. Brighteners containing 2-benzimidazolyl, 2-benzoxazolyl or 2-benzothiazolyl groups. AQ =anion.
Su bstituents
H3
n
Ref.
n3
n
I
OH
-
R - H
R C1
OH
(124)
However, brighteners of this type, e.g. (125)11461 and
f 126)Li471,
have not become important, because in the first
place their effect is somewhat smaller than that of the 1,2,3-triazol-2-yl analogs (97) and ( 115) and, secondly, they are considerably harder to prepare.
SO~H
R = H
R = C(CH&
H = COOCH,
SO~H
H = H
R = CH,
3.6. Conjugated Systems Containing 1,2,4-Triazol-l-yl Groups
7-(I ,2,4-Triazol-l -yl)coumarins, e. g. (127) are formed on
treatment of 7-hydrazinocoumarins with formamide or diacetamide.
R
=
CsHs
C H3
(127) can be quaternized on the triazolyl group and then
used as a brightener for p ~ l y a c r y l o n i t r i l e ~Stilbene
' ~ ~ ~ . derivatives containing sulfo groups and 1,2,4-triazoI-l -yl groups have
also been
3.7. Conjugated SystemsContaining 2-Benzimidazolyl, 2,Benzoxazolyl, or 2-Benzothiazolyl Groups
Although so far conjugated systems containing monocyclic
2-imidazolyl, 2-oxazolylfi'I, or 2-thiazolyl groups have been
of no industrial importance, numerous optical brighteners
arederived from the benzo- or naphtho-annelated derivatives.
More than 600 patents record such compounds, their main
use being to provide white shades on synthetic fibers and
plastics. Examples are collected in Table 5.
Angew. C h m . inrrmar. E d i t .
Vol. 14 ( 1 9 7 5 ) 1 No. 1 0
Many carbocyclic or heterocyclic systems that, like benzoxazole, themselves fluoresce weakly, are converted on combination with a 2-benzoxazolyl group into compounds showing
outstanding fluorescence. There the benzoxazole produces not
only an extension of the resonating system but also a lowering
of the Sm*level below the usual lowest Tnp* level of double
bond systems with a distinct decrease in the life of the excited
singlet. The combination of these two effects leads to fluorescence[' 69!
673
3.7.1. Aqueous Acids as Cyclizing Agents
Aqueous acids can be used only in the synthesis of 2-benzimidazolyl derivatives. Good yields are obtained in, e. g., the
reaction of o-phenylenediamines with carboxylic acids in 40 %
sulfuric acid['521or in 85 % phosphoric
i 132)
It is also possible to treat a carbonyl chloride (produced
in some cases in ~ i t u [ " ~ ]with
)
the amine component, and
then to cyclize the resulting amide (after isolation, if necessary)
by addition of the catalyst[154*1 5 8 - 16'* 173! Compounds
(Z33)-(Z35) are examples of this (for solvents see references[ 1 7 3.119 - 1831)
NHz
NH
I
R
HOW-(C€iOH),-COOli
8 5 5 H,PO,
*
Qf!\WND
N
I
R
N
R
Water can be removed from the malic acid derivatives
(128), yielding (229), by heating in tetralin11521or by treatment with urea in glacial acetic
3.7.2. Polyphosphoric Acid (PPA) as Cyclizing Agent
PPA containing 85 % of P,05 is a n efficient cyclizing agent
for the synthesis of benzazoles. By means of PPA, monoor dicarboxylic acids and their amides, esters, or nitriles can
beconvertedinto benzazolessuchas (130)[1721,and(131)r1741
on treatment with o-phenylenediamines, o-aminophenols, oaminophenyl ethers or o-aminothiophenols at 100-200 "C
with exclusion ofair[lsl*158. l 7 l * 72! The limits of this reaction
are set by the sensitivity of the reactants to PPA.
A particularly elegant variation is to treat equimolar
amounts of carboxylic acid and amine components by stepwise
heating in solvents while the water produced is distilled
off[179. 1841.
3.7.4. Oxidative Ring Closures
Schiff bases from o-aminophenols or o-phenylenediamines
and aromatic aldehydes can be oxidized to benzoxazoles and
benzimidazoles, respectively, in inert solvents by means of
chloranil[1641,sodium nitrite in glacial acetic acid[Is5], potassium permanganate['861, or lead(1v) salts[187!
n
(131)
R = H , CH3, R ' = H, CzH,
3.7s.3. Boric Acid, Toluenesulfonic Acid, or Zinc Chloride as
Cyclizing Agent
Problems of corrosion can be decreased by replacing the
PPA for removal of water with boric acid, toluenesulfonic
acid, or zinc chloride in an inert solvent as the catalyst. Ring
closure to compounds of type (132) occurs as formulated.
In practice, equimolar amounts of the carboxylic acid or
its ester for example, can be melted together with the amine
component at 180-200°C with exclusion of air[162.
674
This oxidative ring closure succeeds even with N-arylamidinium salts (136), although with only moderate yields.
~HN;c+<Ho
omn
Pb( 0 - C 0 - C H J ) ~
*
2 IiCl
' N
H
C6H6
H
H
Angew. Chem. internat. Edit.
H
/ Vol. 14 (1975) / No. 10
Table 6. Brighteners containing 1,3.4-oxadiazolylgroups.
3.7.5. Reductive Ring Closures
Ring closure of derivatives of o-nitroanilines[”’* I 9 O 1 or onitrophenols[lB9.I 9 l 1 , to benzimidazoles such as (137) or benzoxazoles such as (138)., respectively, under reducing conditions can also be effected.
(137)
02N0cH3
’
Pd/C, FeCI,
o.
~
CO, 527 bar
1,2,4-Oxadiazoles such as (142) and (143) were only
recently used as building units for optical brighteners; they
have the fluorescingsystem attached to C-3 or C-5. The cyclization is effected in nitrobenzene.
( 138)
3.7.6. Benzoxazoles from o-Haloanilides
In recent years benzoxazole syntheses have been described
that start from o-haloanilides. These compounds are heated
with copper salts in the presence of bases, yielding the desired
compounds (139) and (140).
Ii
W ) - C H = C H - ( N
0D
‘ 0
3.9. Conjugated Systems Containing Triazinylamino Group
3.8. Conjugated Systems Containing 1,3,4-Oxadiazole-l,2,4Oxadiazole, or 1,3,4-Thiadiazole Derivatives
1.3,4-Oxadiazole derivatives are often mentioned in the
patent literature as components in optical brighteners. 1,3,4Oxadiazoles (141) are obtained on removing water from diacylhydrazines e. g. with thionyl chloride, oleum, or phosphorus oxychloride.
-1120
R-CO-NH-NH-CO-R
N-N
Rqo>R
(141)
Treatment of diacylhydrazines with P,S, or P,S5 yields
1,3,4-thiadiazolederivatives. Table 6 shows a selection of 1,3,4oxadiazoles.
Anguw. Chem. inrrmur.
Edir. 1 Vul. 14 ( 1 9 7 5 ) 1 Nu. I0
While simple acylation products of flavic acid, e. 9. those
given by substituted benzoyl chlorides[2o6]or phenyl iso~ y a n a t e [ ~ ~have
’ ~ , lost their importance, products acylated
by the s-triazino group (144/[2081
have become dominant. The
almost unlimited number of combinations of the substituents
R’-R4 permits satisfaction of almost any demand over a very
broad spectrum of industrial uses. Table 7 gives a collection of
characteristic compounds of this class.
Triazinylflavic acid derivatives ( 1 4 4 ) are prepared industrially by treating 2,4,6-trichloro-1,3,5-triazine
(cyanuric chloride) with flavic acid and any desired amine, ammonia, or
alcohol-in the case of the amines in an aqueous medium
and without isolation of the
The bond
strength between the chlorine atoms to be exchanged and
the triazine ring depends on the nucleophilic character of
the other substituents; this makes it possible to carry out
an industrial one-step process in such a way that no disturbing
yellowish to greenish by-products are formed, e. 9. by coupling
of two stilbenyl groups to one triazinyl group. The cyanuric
chloride is thus usually treated with flavic acid only in the
second stageF219!
675
Table 7. Brighteners of type ( 1 4 4 ) containing s-triazinylamino groups.
n3
K'
IN(CH,CH,-OH)z
N(CH , - € H ,OH),
NH+CH 2)2-S03H
N(CH3-CH2-CH2-SO3H
c1
OCH,
O+CH2)Z--O--CH3
NH--C6H5
NHZ
NH-C6HS
N(CH,-CH,-OH)2
NH-C,HS
morpholino
NH33s03H
N(CH ,<H
NH-C6H,
,OH),
OCH3
/CH,--CHz-CN
N
\CH,--CH(OH)-CH,
polyamide
cellulose, wool.
silk, cotton
paper coating
(casein)
cellulose
(euhaustion process)
polyamide. cellulose
fabrics made from mixed fibers
detergent for
cellulose
cellulose (Foulard
process), paper pulp
polyamide, cotton
cellulose, acidresistant
c2 171
S03H
The aminocoumarins (24) and (20) can also be acylated
by cyanuric chloride, yielding (145) and (146), respectively.
On exchange of the chlorine atom for a diethylamino group,
the plastic brighteners (247)[2201and (248)[2211are obtained.
3.10. Conjugated Systems Containing s-Triazin-2-yl Groups
Treatment of 4,4'-stilbenedicarbonyl dichloride with benzonitrile and ammonium chloride in odichlorobenzene in
the presence of aluminum chloride gives the bis(triaziny1)derivative (149)12221.This high-melting compound is suitable as
a brightener for polyesters that are to be spun.
H5C6
C6H5
The synthesis of dimethoxy(pyreny1)-s-triazine (251 ) proceeds ditrerently: for example, cautious treatment of pyrene
with cyanuric chloride in the presence of aluminum chloride
gives(l50), whose remaining chlorine atoms are finally replaced by methoxy g r o u p ~ ~ ~ ~ ~ ] .
"
676
4. Conclusion
Optical brighteners are used in four areas: as constituents
in detergents, for whitening paper, for textile finishing, and
for the brightening of plastics and paints. The demands on
a brightener intended to improve the appearance of cotton
and polyamide in the washing process are dictated by the
local washing habits. Brighteners are required that will be
withdrawn from the alkaline wash bath at the boiling point,
at 5O-6O0C, or at room temperature; the brighteners should
be stable to peroxides and often to hypochlorite bleach solutions. Other important characteristics of brighteners used in
washing machines-and the same applies equally to all areas
of application-are naturally also easy availability and thus
a favorable price. These demands are met partly by triazinylflavic acid derivatives of type (244) and partly by triazolylstilbenesulfonic acid derivatives such as (84), (89), or (97)[224!
In the paper industry too, it would no longer be conceivable
to dispense with whiteners. They are either added to the
paper pulp or applied by means of a starch or casein-containing
surface layer. Suitable paper whiteners have proved to be,
here too, triazinylflavicacid derivatives of type (144), particularly those that are unaffected by fillers such as China clay
and are as acid-resistant as possible.
The type of the brightener used in textile finishing varies
with the material to be treated; representatives of all the
classes of compounds discussed above will be encountered.
For brightening cotton, the most important textile fiber,
compounds of type (144) are again used, for improved cotton
the triazolylstilbenedisulfonic acid derivative (98) is particularly suitable. Polyamides are advantageously brightened by
derivatives of 2-pyrazoline containing sulfonic acid, sulfonamide, or alkylsulfonyl groups, by triazinylflavicacid derivatives
of type (144), or by (97). Derivatives of 2-pyrazoline and
bis(benzoxazoly1)thiophene are available to produce whites
on cellulose acetate fibers. These brighteners and also derivatives of naphthalimide, of bis(benzimidazoly1)furanand of coumarin, particularly those containing basic groups, are suitable
for brightening polyacrylonitrile.
Angew. Chrm. i n t r m a t . Edit.
/ VoL 1 4 ( 1 9 7 5 ) / No. 10
In keeping with the importance of polyester fibers a wide
choice of brighteners for this material is a ~ a i l a b l e [ ~Among
~~l.
them we find stilbene derivatives such as (90), naphthalimide
derivatives such as ( 3 9 ) and (40), as well as coumarin derivatives and numerous brighteners containing benzoxazolyl
groups.
Wholly synthetic fibers can also be brightened during the
spinning process, and this is probably the technically most
elegant process. Again among the brighteners applied during
spinning-these must be particularly fast to light and stable
at elevated temperatures-we find representatives of the most
varied types of compounds, namely compounds of type ( 1 4 4 )
(as free sulfonic acids) for brightening polyamide, 2-pyrazoline
derivatives for brightening cellulose acetates, polyamide, or
polyacrylonitrile, and benzoxazolylstilbene, benzoxazolylnaphthalene, and coumarin derivatives such as (94) for brightening polyester fibers. The situation for plastics brighteners is
very similar.
Optical brighteners have been used for about 30 years without any harmful side effects having been reported. Nevertheless, it is only recently that ecological and toxicological doubts
about these products, which are especially easily detected
because of their fluorescence, were disposed of at a scientific
Hearing in Stockholm[z26~.
In this review it has been possible to discuss only a selection
from the chemistry of brighteners. The diversity of classes
of brighteners and the matching of individual products to
industrial requirements have been possible only because of
the great variety of heterocyclic chemistry.
Received: July 1, 1975 [A 81 IE]
German version: Angew. Chem. 87, 693 (1975)
Translated by Express Translation Service, London
_____
[ l ] S. Petersen, Angew. Chem. 61, 17 (1949).
[2] R . Zweidler, Textilveredlung 4, 75 (1969); A. K . Sarkar: Fluorescent
Whitening Agents. Merrow Publishing Co. Ltd., Watford 1971; H.
Gold in K . Venkataraman: The Chemistry of Synthetic Dyes. Academic
Press, New York 1971, Vol. 5, pp. 535ff.
131 Austrian Pat. 175871 (1950). Sandoz; DBP 842074 (1946), Ciba, Inv.
F. Ackermann; DBP 946449 (1952). Bayer, Inv. H . Gold and S. Petersen.
[4] B. N . Martoo, Trans. Faraday Soc. 52, 1184 (1956); C . E. Wheelock,
J. Am. Chem. Soc. 81, 1348 (1959); H . Umemoto, T Kifano, and K .
Konishi, Kogyo Kagaku Zasshi 73, 1146 (1970).
P. 1. Petrouich and N . A. Boriseoick, Isv. Akad. Nauk SSSR, Ser.
Fiz. 27, 703 (1963).
DBP I262206 (1961). Bayer, Inv. R . Raue and A. Brack.
DBP 1222014 (1960), Ciba, Inv. E. A. Siegrist, P. Liechti, and M .
Dunnenberger.
H. Umemoto er a/. Kogyo Kagaku Zasshi 74, 2123 (1971).
USSR-Pat. 186501 (1965), Inv. P. I. Petrouich and A. G . Emel‘yanou.
DBP 1090624 (19551, Inv. R . Raue ef a/.: USSR-Pat. 165750 (1963),
lnv. P. I. Petrouich.
DBP 1275983 (1956), BASF, Inv. F. Miihlbauer et a/.
French Pat. 1565731 (1967). Hickson & Welch.
J R Johnson. Org. React. I. 210(/942).
DBP 1 102694 (l960), Bayer, Inv. R. R a w .
US-Pat. 3351482(1965),Bayer, Inv. R . Raue: Belg. Pat. 703813 (1966).
Hickson &Welch, Inv. A. K . Sarkar.
DOS 2240037 (1971), Ciba-Geigy, Inv. P. Liechti.
DBP 1296 121 (1961). Bayer, Inv. R . Raue and H. Gold; DOS 2329991,
2355 116 (19721, Ciba-Geigy, Inv. H . Schliipfer.
J . R . Johnson. Org. React. I, 226 (1942).
W E. Solodar and M . Green, J. Org. Chem. 23, 103 (1958); E. Proft
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DBP 1020636 (1955). Geigy, lnv. H . Hiiusermann.
J . J . Blanksma, Rec. Trav. Chim. Pays-Bas 29,408 (1910).
US-Pat. 3514471 (1968). Showa Chem. Ind., Inv. 7: Yanagisawa and
0 . K oroyori.
DOS 1793262 (1968), fnv. H . Knupfer and C.-W Schellhammer.
N . K Subba Roo and K Sundaramurthy, Proc. Indian Acad. Sci., Sect.
A S4, 321 (1961).
A. A. Goldberg and R . S. Theobald, J. Chem. Soc. 1954, 2641; H.
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Angew. Chrm. internat. Edit. 1 Vol. 14 ( 1 9 7 5 ) No. 10
[26] DBP 1293160 (1964), Bayer, Inv. C.-W Schellhammer, K.-W Muller,
and R. Raue.
“71 S . Sethna and R . Pharfke, Org. React. 7. 1 (1953).
[28] Czechoslovak Pat. 141903 (1968), Inv. J . Pirkl.
[29] US-Pat. 3322794 (1964), Geigy, Inv. J. Haeberli.
[30] US-Pat. 3356689 (1966), Geigy, Inv. J . Hoeherli.
[31] US-Pat. 2616855 (1952). Procter & Gamble. Inv. C. E. Wheelock.
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[33] DAS 1278385 (1965), Bayer, Inv. H . Knupfer et a/.
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C.-W Schellhammer.
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1391 DAS 1419329 (1962), Hoechst, Inv. E. Schinzel and K . - H . Lebkiicher.
[40] DOS 201 1552 (1970), 2142564 (1971), Hoechst, Inv. H. Mengler, E.
Schinzel,and G.Riisch;DOS2145019(1971),Hoechst, Inv. H. Mengler.
[41] US-Pat. 3378389(1962),Bayer, Inv. C.-W Schellhamrnerand A. Wagner;
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[42] Netherlands Pat. 6906448 (1959). Bayer.
[43] Brit. Pat. 1209631 (1967). ICI, Inv. G. H. Keats.
1441 DOS 2050725 (1970), Bayer, Inv. C. Boehmke and H. Theidel.
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G. R. H. Mingasson, and R. F. M. Sureau.
1471 DOS 1670980 (1968), Bayer, Inv. M . Hajek.
[48] DOS 1670988 (1968). Bayer, Inv. M. Hajek.
[49] DOS 1695 103 (1966). Ciba, Inv. S. Rosenberger, E. Troxler, and H.
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[SO] DOS 1802642 (1967), Ciba, Inv. E . Troxler and H. Hiiusermann.
[Sl] DOS 2235073 (1971). Sandoz, Inv. F . Fleck, P. S. Littlewood, and
A. K Mercer.
DOS 2248772 (1971), Sandoz, Inv. H. Aebli.
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Scheuermann.
DOS 2217259 (1971), Ciba, Inv. M . Stagi.
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DOS 1923702 (1969). Hoechst. Inv. H . Men& e f a / . : DOS 1904424
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Bayer, Inv. J . Schroeder and C.-W Schellhammer.
US-Pat. 2600080 (1946). GAF. Inv. M . 0. Shrader; DBP 1019274
( I 953). BASF. Inv. E. TolksdorL F. Schubert, and E. Kern; DBP 1023 169
(l958), BASF, Inv. E. Tolksdod F. Schubert, and E . Kern; DBP 1068260
(l959), BASF, lnv. E. Hold.
Jap. Pat. 6515468 (1962), Mitsubishi. Inv. J . Okada and I . Yasuda.
DOS 1445961 (1961), Mitsubishi, Inv. I: Kasai et a / . ; DOS 1419350
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Jap. Pat. 7 113963 (1968). Mitsubishi, Inv. S. Kasai.
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and M . Kaneko.
DOS 2064159 (1969), Sumitomo, Inv. S. Hofra and 7: Akamatsu;
DOS 2043662 (1970), BASF, Inv. H . Scheuermann.
Jap. Pat. 7 134509, Jap. Pat. 7 138418 (1968). Mitsubishi, Inv. H. Okada,
S. (mahori, and S. Hirako.
Jab. Pat. 7213382 (19671, Teijin Ltd., Inv. F. Takabayashi and N .
lto.
Jap. Pat. 7002672, Jap. Pat. 6918955 (1967). Nippon Kayaku, Inv.
7: Noguchi and K . Tsukamoto; Jap. Pat. 7227777 (1969). Mitsubishi,
Inv. H . Okada and S. lmahori; Jap. Pat. 7213383 (1967), Teijin Ltd.
Jap. Pat. 7223706(1968),Nippon Kayaku, Inv. 7: Noguchi, K . Tsukamoro. and 7: Matsunagu; Jap. Pat. 7142506 (1968). Mitsubishi. Inv H.
Okada and M. Kaneko.
DOS 1470051 (1963). Mitsubishi, Inv. H. Senshu and M . Yamashito.
Jap. Pat. 6820971 (1964). Seisan Kaihatsu, Inv. R. Kimura and 7:
Yabuuchi.
Jap. Pat. 7035595 (1967), Nippon Kayaku, Inv. 7: Noguchi and 7:
Matsunaga; DOS 1928286 (1969), Mitsubishi, Inv. H . Okada el al.
DOS 1939620 (1969). Ugine Kuhlmann, Inv. G. R. H. Mingasson.
Jap. Pat. 6918957, Jap. Pat. 7002674 (1967). Nippon Kayaku.
677
1771 Jap. Pat. 6918956(1967),Nippon Kayaku, Inv. 7: Noguchi, K. Tsukamofo. and D. Motsimaga.
[78] French Pat. 1 541 OSO(1967). Ugine Kuhlmann, Inv. G . R . H . M i n g a s s m
l'f
a/.
[79] DOS 1795091 (1967). Ugine Kuhlmann. Inv. G. R . H . Minqaswi
and A. Domergue.
[SO] French Pat. l557945( 1968).Nippon Kayaku; Jap. Pat. 7002668 (1967),
Nippon Kayaku, Inv. 7: Noguchi and D. Marsunaga.
[XI] D O S 1419350 (1962), Mitsubishi, Inv. 7: Kasai el a/.
[82] Review: H. Gold in K . Venkararaman: The Chemistry of Synthetic
Dyes. Academic Press, New York 1971, Vol. 5, p. 620.
1831 DOS 2242513 (1972). Hoechst, Inv. W Deucker and H . Triisrer; DOS
2302372 (1973). Hoechst, Inv. W Deucker and H . Poster.
[84] Jap. Pat. 7308309 (1971). Mitsubishi, Inv. H. Okada and M. Kaneko.
[SS] Belg. Pat. 612955 (1961). 7: Kusai.
1861 M. Okazaki er a/.. Yiiki Gosei Kagaku Kynkai Shi 14, 455 (1956).
I871 7: Kasai and K . Himeno, Kogyo Kagaku Zasshi 72, I128 (1969).
Jap. Pat. 7405333 (1969). Nippon Kagaku, Inv. 7: Noguchi and S.
Mafsunaga.
DAS 1 154799 (1962). Hoechst, Inv. H. Sieber.
K . Oka, 7: Hinohara, and K. Matsui, Kogyo Kagaku Zasshi 71. 1010
(1968).
D O S 2105305 (1971), Hoechst, Inv. W Sahm, E. Schinzel, and G .
Rosch.
DOS 2306515 (1973), Bayer, Inv. P. Hartmann.
Brit. Pat. 871 351 (1956), 0. Dann.
French Pat. 1558762 (1967), Bayer.
US-Pat. 2980549 (1956). GAF, Inv. E. Craig.
DAS I 1 1 1 188 (1959), Hoechst, Inv. W Koller and P. Schlack.
DBP 1087609 (1957). Geigy, Inv. A. F. Daglish, P. Vonderwahl, and
G . A. Tollotson.
DBP I222885 (1962), Bayer, Inv. G. Wolfrum er a/.
DAS 1253275 (1961), Ciba, Inv. E. Marter.
G. Gonis and E. D. Amstutz, J. Org. Chem. 27, 2947 (1962).
US-Pat. 2900386 (1956). Henkel, Inv. B. Raecke ef a/.
Belg. Pat. 611 897 (1960), Ciba; Swiss. Pat. 437347 (1961), Ciba, Inv.
P. Liechti, A. E. Siegrisr, and E. Maeder.
DBP 1276588(1961),Geigy, Inv. H. Huusermann: French Pat. 1320597
(1961), Geigy.
DOS 1942926(1969),Bayer,Inv.C.-WSchellhammer;US-Pat.3663560
(1967). Bayer, Inv. C.-W Schellhammer, A. Dorlars, and W-D. Wirth;
DOS 2040189 (1970), Bayer, Inv. A. Dorlars and H. Gold.
DBP 1469220 (1964). Bayer, Inv. C.-W Schellhammer and A. Wagner.
DBP 1594850 (1967), Bayer, Inv. A. Dorlars and 0.Neuner.
DOS 2 131 788 (1971). Bayer, Inv. J. Schroeder and C.-W Schellhammer.
DOS 1932256 (1968), Geigy, Inv. G. Kabas and R. Zweidler.
DOS 1931 757 (l968), Geigy, Inv. J . A. Gurney.
Brit. Pat. I 200852(1968),Bayer,Inv. U . Ferzer and C.-W Schellhammer.
D O S 16951 19 (1967). Geigy. Inv. H. Hausermann and E. Troxler.
[ I I 1 a] Information about triazoles will be found in review articles: F. R.
Benson and W L. Sacell, Chem. Rev. 46. I (1950); 7: L. Gilchrisr
and G . E. Gymer. Advan. Heterocycl. Chem. 16, 33 (1974).
[ I 121 DBP 1008248 (19551, Bayer. Inv. H. Gold and 0. BaTer.
[112a] Cf. Houben-Weyl: Methoden der Organischen Chemie. Thieme,
Stuttgart 1965. 1. Edit.. Vol. X/3, pp. 809f.
[I131 DAS 1282591 (1963), Bayer, Inv. C.-W Schellhammer, R. Raue, and
H. Gold.
[ I 141 DBP 91 I368 (1948), Bayer, Inv. H . Gold and S. Petersen.
[ I 151 DBP 942395 (1951), Geigy. Inv. E. Keller, R. Zweidler, and H. Hausermann.
[116] DBP I052405 (19561, Geigy. Inv. R. Zweidler and E. Keller; Belg.
Pat. 664606 (1964), Geigy; DBP 1220381 (1960): GAF, Inv. A. F .
Strobel and S. C. Catino.
[116a] DBP 1065838(1957),Geigy,Inv. H. Hausermann; DBP 846849(1948),
Geigy, Inv. H. Hausermann and R. Zweidler; DAS 1218436 (1961),
GAF. Inv. J . A. Cofrancesco.
[ I 16bl DBP 955686 (1952), Geigy, Inv. R. Zweidler and E. Keller.
[I171 US-Pat. 3157644 (19561, GAF. Inv. F . Marschall, H . B. Freyermufh,
and W W Williams: DOS 2148017. DOS 2148018, DOS 2148512
(1970). Ciba-Geigy. Inv. A. E. Siegrist.
[ I 181 A. E. Siegrisf, Helv. Chim. Acta 50,906 (1967). and further communications.
I1191 DBP I234224 (1963), Sandoz, Inv. F. Fleck, H. Balzer, and H . Aebli.
[I201 D O S I470242 (1962). Sandoz, Inv. F. Fleck, H. Balzer. and H . Aebli.
11211 DOS 1519471 (1965). Bayer, Inv. W-D. Wirth, H. Knupfer. and C.-W
Schellhammer.
[I221 DOS 1519461 (1965). Bayer. Inv. A. Dorlars, 0.Neuner, and R. Putter.
[123] DBP 1279636 (1965), Bayer, Inv. A. Dorlars. 0.Neuner, and R. Putter.
[I241 French Pat. 1567496 (1967). Bayer, Inv. A. Dorlars and 0. Neuner.
[I251 DOS 2213754 (1971), Ciba-Geigy, Inv. G . Kabas. H. Schlapfer, and
1. Fletcher.
[ 1261 DBP 1 287 550 ( I 966). Bayer, Inv. A. Dorlars and 0.Neuner.
[126a] DOS 2032 172 (1970). Bayer, Inv. A. Dorlars and 0. Neuner.
11271 H. c. Pechmann, Liebigs Ann. Chem. 262, 270 (1891).
678
[128] DBP 1168437 (1962). Hoechst. Inv. R. Mohr and M. Zimmermann.
[I291 US-Pat. 3697596, US-Pat. 3697597 (1968). Bayer, Inv. A. Dorlars.
[I301 DBP 1670914 (1967), Bayer, Inv. A. Dorlars and 0. Neuner; DOS
2242784 (1972), Bayer, Inv. H. Gold and U . Claussen.
11.311 DOS2210261 (l972), Bayer. Inv. U . C1uirs.sen.H.Gold.and J.Schroeder.
11321 D O S 1695122 (1967), Geigy. Inv. R. Kirchmayr, H. Heller, and
J . Rody.
[I331 DOS 2029096, DOS 2029142, DOS 2029157 (1969). Geigy. lnv. R.
Kirchmayr and H. Schlapfer.
[134] 0. Neuner, Bayer. unpublished.
[135] DOS 2112198 (1970). Ciba-Geigy, Inv. R. Kirchmayr.
[I361 DOS 2213839 (1971). Ciba-Geigy, Inv. G. Kabas. H. Schlapfer, and
I . Fletcher.
[136a] DOS I795073 (1967), Ciba-Geigy, lnv. K. Weber et a!.
[136b] DOS 2258276 (1972). Bayer, lnv. A. Dorlars and 0. Neuner.
[136c] DAS 1108219 (1959). BASF, Inv. W Stilz and H . Pommer; DAS
1112072 (1959), BASF, Inv. W Stilz. H. Pommer. and K.-H. Kdnig.
[137] DAS 1794396 (1966). Bayer, Inv. 0.Neuner ef a/.
[137a] US-Pat. 3869469 (19721, Bayer. Inv. 0. Neuner and A. Dorlars.
[I381 DOS 2159797 (1970), Ciba-Geigy, Inv. R. Zweidler er a/.
[I391 DOS 1670969 (1968), Bayer, Inv. A. Dorlars and W-D. Wirth.
[I401 DOS 2037854 (1970), Bayer, Inv. A. Dorlars and C.-W Schellhammer.
[141] DOS 1670999 (1968), Bayer, Inv. A. Dorlars. C.-W Sehellhammer,
and W.D. Wirth.
[I421 DOS 2335218 (1973). Bayer, Inv. J. Schroeder.
[I431 DOS 2226524 (1972), Bayer, Inv. A. Dorlars, A. Vogel, and C.-W
Schellhammer.
[I441 DOS 1670810(1967), Bayer. Inv. A. Dorlars and C.-W Schellhammer.
[144a] DOS 2310123 (1973). Bayer. Inv. A. Dorlars.
[I451 Cf. R. Puffer in Houben-Weyl: Methoden der Organischen Chemie.
Thieme. Stuttgart 1965 1. Edit.. Vol. X/3, pp, 185K.
[I461 DOS 2062383 (1969), Sandoz, Inv. H. Balzer et ul.
[I471 US-Pat. 3686202 (1968), Ciba-Geigy, Inv. R. Kirchmayr and J . Rod)'.
[148] French Pat. 1551662 (1967), Bayer, Inv. C.-W Schellhammer.
[I491 DOS 1919209 (1969). Hoechst, Inv. A. Horn, E. Schinzel, and G.
Rosch.
[150] DOS 2050771 (1969), Sumitomo. Inv. M. Mafsuo, S. Sagaguchi, and
7: Akamatsu.
[ISl] DAS I105423 (1958), Ciba, Inv. M. Dunnenberger and A. E. Siegrist.
11521 DAS 1039064 (1954). Ciba, Inv. A. E. Siegrisf and F. Ackermann.
[I531 DAS 10% 167 (1957). Ciba, Inv. M. Dunnenberger and A. E. Siegrist.
[154] DAS 1090214 (1955), Ciba, Inv. F . Ackermunn and A. E. Siegrisr:
DAS 1040555 (1956), Ciba, Inv. F. Ackermonn, M. Dunnenberger,
and A. E. Siegrist.
[I551 DOS 1419312 (1960), Daito Chem. Ind., Inv. K. Konishi ef a / .
11561 French Pat. 1336949 (1961). Mitsui.
[I571 US-Pat. 3597364(1962),MitsuiToatsu, Inv. I. Okubo and M . Tsujimoto.
[lSS] DAS 1166197 (l959), Ciba, Inv. M. Dunnenberger, A. E. Siegrisf,
and E. Maeder.
[I591 Swiss Pat. 439292, Swiss. Pat. 492818 (1961), Ciba, lnv. E. Maeder,
P. Liechti, A. E. Siegrist, and M . Dunnenberger.
11601 DOS I795602 (1966/67), Hoechst, Inv. H . Frischkorn. U . Pintschorius,
and H. Mehrmhruch; DOS I 745622 (1966). Hoechst, Inv. H. Frischkorn,
U . Pinf.schorius,and H . Behrenhruch.
[161] DAS 1594855 (1967), Hoechst, Inv. G. Riisch, E. Schinzel, and 0.
Smerz.
11621 DAS 1086237 (1958). Ciba, Inv. M. Diinnenberger and A. E. Siegrisf.
[163] DAS 1147232 (1958), Ciba, Inv. M. Dunnenberger, A. E. Siegrisr,
and E . Maeder.
[I641 DOS 1469227 (1964), Bayer, Inv. H. Harnisch and R. Raue: DOS
1545846 (19653, Bayer. Inv. H . Harnisch and R. Raue.
[I651 Brit. Pat. 736452 (1952), Geigy.
[166] DAS 1089721 (1959). BASF. lnv. H. Bulli e f 01.. DAS 1144280(1961),
BASF, Inv. M. Seefelder and H. G. Reppe.
[I671 DAS l445694(l962), Kodak, Inv. D. G . Hrdberg er a/., DAS 1445699
(1963). Kodak, Inv. M. S. Bloom.
[I681 Austrian Pat. 270567 (1965). Ciba.
[I691 A. Reiser er al., J. Am. Chern. SOC.94, 2414 (1972).
[170] DAS 1067441 (1957), Ciba, Inv. A. E. Siegrisr.
[171] US-Pat. 2985611 (1956),Am.Cyanamid, Inv. D. W Hein, R. J. Alheim,
and J. J. Leauiff; Jap. Pal. 7001891 (1965). Osaka Seika, Inv. 7:
Rmeguwa and S. Iono; DDR-Pat. 94998 (1971), J . Liebscher and
H . Harrmann; Jap. Pat. 7138417 (1968). Showa Chem. Ind., Inv. K.
Matsui, K. Oraguro, and E. Kobayashi.
[I721 Belg. Pat. 717988 (1967). Hoechst.
[173] DOS 2344841 (l972), Ciba-Geigy, Inv. K. Weber.
11741 DAS 1288608 (1963), Sumitomo. Inv. 7: Kinoshira.
[I751 DAS 1109177 (1958). Ciba, Inv. M. Dunnenberger. A. E. Siegrist,
and E. Maeder.
11761 DOS 1519486 (1964). Nippon Kayaku, Inv. N. Ono. S. Serizawa.
and M. Sumifuni.
11771 French Pat. I532087 (1966). Hoechst.
[I781 DOS 1594830 (1965). Ciba. Inv. E. Maeder and A. E. Siegrisr.
11791 DOS I949334 11968). Ciba, Inv. E. Marter.
Angew. Chem. inrernar. Edit. 1 Val. 14 ( 1 9 7 5 ) 1 No. 10
[180] DAS 1253222 (1962). Ciba. lnv. E. Maeder ef a / .
El811 DOS 2237874 (1971), Ciba. Inv. H. R. Meyer.
11821 DOS I470289 (1963). Sumitomo, Inv. M. Ohkawa. E Yumukuwa, and
7: Kinoshifu.
11831 Jap. Pat. 6830193 (1965), Nisso Chem. Ind., Inv. G. Huyukawu and
G . Mochizuki.
[I841 DOS 1795157 (1967),Ciba, Inv. E. M a f f e r .
[I851 US-Pat. 3341 529 (1964). Am. Cyanamid, Inv. B. G. Buell.
11861 US-Pat. 3767663 (1970). Am. Cyanamid, Inv. H. X. Kaempfen and
s. County.
[I871 DOS 2230077 (1971), Morton Norwich Prod., Inv. K . J , Hayes.
[188] US-Pat. 3206468 (1968). Merck Co., Inv. !I J. Grenda.
[ISY] DOS 2047998 (1969), Am. Cyanamid, Inv. A. G . Mohan and R. K .
Madison.
[I901 DOS 2159469 (1970). Ciba. Inv. H. Schliipfer.
[I911 DAS 1232922 (1960), Ciba. Inv. M. Dunnenberger ef a / .
[I921 DAS 1445861 (1961). Hodogaya, Inv. M . Lizecku ef a / .
[I931 DOS 2003575 (1969). Am. Cyanamid. inv. If. X. Kaempfen.
[I941 Jap. Pat. 7041629 (l967), Osaka Seika, .Inv. S. Jono and 7: Fujino.
[195] Jap. Pat. 7422929 (1967), Osaka Seika.
[196] Jap. Pat. 7041630 (1967). Osaka Seika. Inv. S. Jono and 7: Fujino.
[197] Jap. Pat. 7 108785 (1966). Osaka Seika, Inv. K . Toneyawn. S. Seino,
and 7:FujinotJap. Pat. 6920268 (1966). Osaka Seika, Inv. K . Tonegawa.
J. Jono, and 7: Fujino.
[I981 French Pat. 1445769 (1964)- Ciba.
[199] DOS 2356611 (1972), Ciba, Inv. H . R. Meyer.
12001 DOS 2350570 (1972), Ciba, Inv. H . R. Meyer.
[201] DOS 1594824 (1965). Ciba, Inv. A. E . Siegrisr ef a / .
[202] DAS 1238874 (1962), Ciba, Inv. A. E. Siegrisf er a / .
12031 Brit. Pat. 1 1 15325 (1965), Ciba.
[204] DOS I955374 (1969). BASF. inv. H . Scheurrmann.
[205] D O S I958778 (1969), BASF, Inv. H . Schruermann.
12061 US-Pat. 2089413 (1934), ICI, lnv. C . Proine, J. A. Radlry, and L.
P. Rendel.
[207] D R P 746569 (1940). IG Farbenindustrie, Inv. S. Petersen, 0. Bayer.
and B. Wendt.
[208] D R P 731 558, 752677 (1940), IG Farbenindustrie. Inv. €3. Wendf.
[209] DBP 814902 (1947). ICI, Inv. D. A. W Adams and R. H. Wilson.
[210] DBP 848496 (1949). Ciba, Inv. F . Ackermann; DBP I I83882 (1960),
Bayer, Inv. .I.
Hagemann and W Schdermann.
[211] DBP 1444015 (1963), Bayer, Inv. H. Gold. E. Lehmann, and W Theuer.
[212] D R P 752677 (1940), IG Farbenindustrie, Inv. B. Wendr.
[213] DBP 1119646 (1959), Du Pont, Inv. J. Gessner and R. C. Seyler.
[214] DBP 814901 (1947). ICI, Inv. R. H. Wilson: DBP 859313 (1948).
GAF, Inv. W W Williums and W E. Wallace: DBP 870263 (1951)
Ciba, Inv. F. Ackermann.
[215] DBP 1090168 (1957), Bayer, Inv. J . Hegemann. A. Mirrowsky. and
H. R o o r
[216] Jap. Pat. 5505983 (1955). Nisso Chem. Ind., Inv. G. Huyakawa.
[217] Cf., e . g . , DOS 2430624 (1973). Sandoz. Inv. F. FIeck and H . R. Schmirl.
[218] DBP 1250830 (1963, Bayer, Inv. H . Gold and E. A. Kleinheidr.
12191 Brit. Pat. 1174631 (1967), Bayer, Inv. H. Gold and E. A. Kleinheidr.
[220] DBP 1096909(1957),Geigy,Inv. H . Huusermunn: DBP 1274063 (1964),
Bayer, Inv. 0. Berendes, H . Gold, and C.-W Schellhammer; US-Pat.
3429880 (1965), Geigy, Inv. H . Hiiusermann: US-Pat. 3518266 (1967).
Geigy, Inv. H. Hiiusermann and E. Troxler.
[221] DBP 1249211 (1961), Bayer. Inv. E. Siegel and H. Gold.
[222] DAS 1294922 (1964). Ciba, Inv. A. E. Siegrisf ef a/.
12231 DBP 1273479 (1961), ICI, Inv. J. R. Arkinson and S. Harrley.
12241 K . 4 . Bode, Tenside Deterg. 12. 69 (1975).
[225] H . H e f i , Textilveredlung 4, 94 (1969).
12261 MVC-Report 2: Fluorescent Whitening Agents. Stockholm 1973: cf.
also F. Coulsfon, F. Korre, R. Anliker, and G . Miiller: Environmental
Quality and Safety. Suppl. Vol. 3. Thieme, Stuttgart, in press.
Detection of Fragment Genesis in the Mass Spectrometer:DADI Mass
Spectrometry as an Aid in the Structure Analysis of Organic Compounds
/mahodso/
New analytical
By Urs Peter S c h l u n e g g e r [ * l
“Direct Analysis of Daughter Ions” (DADI) can be carried out with commercial mass spectrometers embodying the Nier-Johnson inverse geometry. DADI measurements permit experimental
detection of the consecutive formation of molecule fragments (fragment genesis). Knowledge
of fragment genesis enables the chemist to clarify the fragmentation processes of molecule-ions
and provides information on the structure of fragments formed in the mass spectrometer.
In combination with classical mass spectrometry such information makes it easier to determine
the structure of compounds, to analyze mixtures, to determine the sequence in periodically
constructed molecules, for example oligopeptides, and to study rearrangement reactions occurring
in the mass spectrometer.
1. introduction
Direct Analysis of Daughter Ions (DADI) was first put
forward by Maurer et a!. in May 1971[’]. In November of
that year Bejmon and Cooks published the same method under
the abbreviated name MAIKES (Mass Analyzed Ion Kinetic
Energy Spectrometry)[21.Both designations attempt to characterize the basis of the method, Beynon’s more from the theoretical standpoint. The abbreviation DAD1 seems to be more
readily understood by the practical chemist and will therefore
be used here. Since DADI mass spectrometry is relatively
young and may not be too well known to chemists, its potential
[*] Priv.-Doz. Dr. U. P. Schlunegger
Organisch-chemisches Institut der Universitat
CH-3000 Bern 9. Freiestrasse 3 (Switzerland)
Angrw. Chem. internur. Edif. 1 Vol. 14 11975) J No. 10
utilization will first be demonstrated for the case of 3-methyl-4phenyl-2-butanone (Fig. 1). The classical mass spectrum (Fig.
2a) of this compound is reproduced as a typical example
in a widely used textbook of organic chemistry[41. In the
discussion of the relationships between structure and mass
spectra the fragment ion at m/e= 147 (M” - 15) is there described as the product of removal of the methyl group u to
thecarbonyl group (Fig. 1 : cleavage site a). O n closer consideration the question arises whether this (M - 15) fragment may
not also arise partially by cleavage of the methyl group from
position 3 (Fig. 1 : cleavage b, P-cleavage relative to the carbony1 group).
Classical mass spectrometry, now used widely as a method
of structure determination in organic compounds, can give
no definite answer in this case, because it is always isolated
679
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