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Substituted benzylidene Cyanines
m
and Rz%=cr~s
Research
Substituted
1 (1980)
161-16,
Note
Benzylidene Cyanides B-N
Depamnent
of Chemrstry,S.P Dumka
JHA (Bhagalpur
College
(S P)-814101.
Unzuersl@),
Bthar, Indta
and J CBANEIRJI Dcpamnent
of Chemlshy, B N College. Puma Puma-800004, Bzhar. Kndla
Unwers~ry,
SUMMARY Eight new condensing
chain substttuted benzylidene cyanine 4-dimethylamino-2’-nitrobenzophenone
dyes and
have been prepared 4-drmethylamzno-3’S’-
by
dmitrobenzophenone with methiodides of quinaldine and 6_haloquinaldines, m absolute ethanol, using pipen’dine as a basic catalyst. The optical absorption and extra sensltisation data of the dyes have been recorded and compared with those of their methin analogues. The dyes absorb at longer wavelengths than thezr unsubstituted analogues, contrary to earlier observations.‘d The dyes obtained from the 2’-nitroketone are good sensitisers, whereas those obtained from the 3’,5’-dinitroketone, are densensitisers
1.
tN-l-R3DUCTION
Although quite a large number of 4-dialkylamino styryl dyes, containing different variously substituted heterocyclic nuclei are reported, and the effect on optlcal absorption and sensitisation of substituents in the hetero part of ‘rhe hemicyanines has been extensively studied,’ very little work has been carried out to study the effect of substituents in the methin chain of the dye Moreover, Q!- and p-methin substitutions in styryl cyanines are mo1ecules.8-” reported to cause a hypsochromic shift in the absorption maxima, when but the extent of the hypsocompared to their unsubstituted analogues,‘-3 chromic shift is less pronounced in the case of P-substituted products.It was 161 ~ye_~and figments England, 1980 Printed an Nor&em
0143-7208/80/0001~161/$02-25-_0 Ireland
Apphed
Science Publishers
Ltd,
162
B
N JHA
J CBANEtRIl
therefore of interest to prepare some ,G-methin substituted styryi cyanines and study thetr opttcal properties systematically_ The p-methtn chain substitution can be effected by using suitable I-pdtalkylamino ketones in place of 4-p-dialkylaminoaldehydes This paper reports the preparation of dyes denved from two ketones, 44-dimethylamtno-3’.5’-dmitrodimethylamino-2’-nitrobenzophenone and benzophenone. whtch were obtained by the method of Shah er al.” with suttable modificattons. The quatemtsed bases required, were prepared by heating the base with methy iodide-l3 The synthesised ketones were separately condensed rn the usual waylJ wtth methtodtdes of qutnaldine” and 6-chloro-. 6-bromoand 6-iodoqutnaldinest3 I6 tn absolute ethanol in the presence of a few drops of ptperidtne to afford etght new dyes (II),,-D2,) as in Scheme 1 The dyes (D,,-D,,) obtained from 4-dtmethylamtno-2’-nttrobenzophenone from 4-dimethylamtno-3’.5’-dinttrobenzophenone are and dyes (D3, -DZ2) htghly crystalline and are mostly dark vrolet m colour. Then- alcoholtc soluttons are either reddish vtolet or violet The colour is reverstbtly dtscharged by addttion of mtneral actds and regenerated on bastficatton, indtcsttve of the charactensttc of cyantne dyes ,!3-Methrn substttutton may affect the resonance stabiltsatron of substttuted dye molecules stertcally and electrontcally. as the substituents under study are electron attracttng. The stenc htndrance to resonance tn the matn conjugated chatn due to bulkrness of the substttuents IS hkely to be significant too. The data for optical absorptton maxima and the ranges of extra sensttisation have been recorded. analysed and compared wtth those of their corresponding styryl analogues wherever posstble and reasonable conclusions have been drawn.
2
covcJ-us10ss
The absorptton ma\tma and extra senstttsatton of the newly prepared dyes and those of thetr styryl analogues. available tn the literature. are shown tn Table 1 for comparison. It ~111 be evident from the absot-ptton data that P-methtn substttutton, whether by 2-nttrophenyl or by 3.5-dtnitrophenyl, has caused an almost untform bathochromtc shift in A,,, by about 30 rnp. It will also be seen that 6-substttution of the heteronucleus has caused only a slight bathochromic shift the order being 6-H < 6-CI < 6-Br < 6-I tn both the 2-nitro senes and tn A,,. the 3.5dmicro sertes Analysts of the sensittsation data. however, does not lead to any definite generalisation The p-2-nitrophenyl dyes are inferior sensitisers to their unsuhstttuted analogues. while the P-3.5-dtmtrophenyl dyes are desensittsers
163
164
BNJHAJCBANEFUI 1
TABLE THE RECORDED
DATA
OF
ABSORPTION DYES
BENZYUDENECYANlNE
M/U5MA
AND
-l-HOSE
D,, D,, D 2” D,, D 71 Dh D 14
578 579 583 569 578 580 583
620 dc, 630 630 650 Da Da D” Da
w. lbvr nu, c rm. c I, Ic
ECl-R4
SENSll-ISAl-ION TITRYL
OF
THE
ANALOGUES
Exfra
sensNzsatzon
klU.S (mw)
range her)
560
530
680
580
11
590 u 590 590 -
548 550 552 530 548 550 552
650 650 650 680 650 650 650
595 595 600 580 595 595 600
16 16 16 11 16 16 16
(mw)
56.4
AND
IJN-
sensrfrsanon
range
D,,
OF
Unsubshtuted styryl dyes Cfrom rhe Lferufure)
Subsntured benzylrdene cyanme dyes Extra
(h,,)
Reference
c connected. I Intense, u unpronounced. w weak, dc &sconnected. Ic loosely connected, ml moderately Intense lbvr Intense In blue-violet range, D desenslt,ser a In all cases, lntenslty m blue-violet range IS decreased The desenslhsmg properry vanes En the order D,,CD,,
3.
ECXPEFUhfJ3J-l-AL
3.1. TIze ketones For the preparation of ketones, the general method amrnobenzophenones and therr substituted products adopted wrth some procedural modifications.
of production of alkylby Shah et al.” was
(I) 4-Dimethylamino-2’-mtrobenzophenone: Dtmethylanihne (8 ml) was added in portions to a mixture of o-nitrobenzanihde (3g) and phosphorus oxychloride (8 ml) and warmed (4045°C) for 8 h. The viscous mass, on extracting with hydrochlonc acid, was almost neutralised with sodium hydroxide solution and rendered homogeneous with alcohol. The ketone, which separated after additton of a few drops more of sodium hydroxtde solution and chilling, was recrystallised from toluene as shining deep orange leaflets (yield 30%. m p. 24%50°C; ref. 12. yield not mentioned, m-p. 251-53°C). (ii) 4-Dimethylamlno-3’,5’-dmltrobenzophenone: 3,5-Dinitrobenzanilide (5 g) and dimethylanihne (7 ml) were mixed together and phosphorus oxychloride (7 ml) was slowly added. The mixture was heated on a steam bath for
6-Iodoquumldtne
Qumaldmc
6Chloroqumaldme
G-Bromoquinaldmc
6-lodoqmnaldmc
D *,,
D,,
D 22
D 21
D zJ
2-p-Dlmetllylamlno(p-2mtrophenyl)styryl qumohne 2-p-Dlmethylamino(/.S2nrrorphenyl) sty1 y&6chloroqumohnc 2-p-Dlmethylammo(p-2. mtrophcnyl) slyryl-6bromoqumohnc 2-p-D~me~hylammo(/3-2. mlrophenyl) slyryl-6~odoqumohne 2-p-Drmcthylannno(p-3,5dmnrophyenyl) styrylqmnolmc 2-p-Dlmethylammo(p-3,5dmrlrophcnyl) styryl6-chloroqumohnc 2-p-Dlmcthylanlmo(p-3,5dmrtrophcnyl) styryl6.bromoqumohnc 2-p-Drmethylammo(p-3,5dmdrophcnyl! styryl-6rodoquinolme dvc wgr
dvc wrl
dv IC wrr
dv IC
dv VI wbr
WTT
dv sn
dv +n wrt
dv IC
CpNal calaur and s/mpP
75
73
71
67
37
41
58
61
Meld (%I
161
231
208
(“Cl
Mp
WIIII
Molecular formula
DENZYLlD@NE CYANIMZ DYES
’ dv dark vlolei, sn small needles, tc tmy crystals, dvc dark violet crystals, wbr wnh blue rellcx, wgr wrr w1t11 red rcflcx, wrl wnh rcddrsh tmgc
6-Bromoqurnakhne
6Chloroqumaldme
Qurnnldmc
Method& of base used
DW
Dul
47
Dye symbol
TABLE 2 ANALYI’ICAL DATA OF THE SUBSTK~J
35.83
33-84
26~31
21-78
38 34
33.58 2841
23~61
7.91
8.4;’
9.08
9462
6.33
6.82 7 35
I.82
35.88
33.88
26 35
21.82
38.31
33 62 28.45
2365
green rcflcx, wrl with rcddlsh IusIrc,
7.86
8.42
9 01
9 51
6 21
6.11 129
I*11
Hal
N
N
Hal
Calc (X)
Fourrd(%)
a
#
1
I m
$
166
B
N .JHA,J
C BANERJl
6 h and then on an oil bath (115-120°C) for a further 4 h. The acid extract of the crude product was neutralised with sodium hydroxide solution and the separated ketone recrystallised from a mixed solvent, ethanol: benzene (3: l), as light orange coloured shining woolly crystals, (yield 40%, m-p. 193-94°C). C,sH,,NL& 3.2.
Found: requires:
Tile quaternary
C, 57-11; H. 4-06; C. 57- 14: H, 4-14:
quinaldmlum
N. 13-28% N, 13.33%
salts
salts were obtamed by adoptmg the general method of preparation of Johnson and Adams.‘3 The bases and methyl iodide (1: l-5 M) were heated In a pressure bottle on a steam bath for 24 h and the product recrystallised from hot water. The
3 3.
quaternised
The
benzyhdene
cyatlrne
dyes
A nuxture, contaming requlslte amounts of the ketone, the quatemary salt. ethanol and a few drops of piperidlne was refluxed mildly under a moisture trap for about 2 h The resulting solution. on cooling. afforded the dye. which was recrystalllsed from methanol The percentage analysis. yield. m p (uncorrected). etc of the dyes are given In Table 2 3.-I Recordttlg of opucal properrres The absorption maxlma of the dyes were recorded on an Beckmann Spectrophotomerer. Model DU In l/1000 ethanolic solutions. The sensitlsatlon spectra were recorded on an Adam Hllger Wedge Spectrograph on Ilford N40 process plates, bathed In dilute ethanol (1 _3) solutions (l/50 000) of dyes. The plates after -t min bathing were dried. exposed for 4 mm to light from a 150 c-p point-o-hte lamp
AChNOWLEDGEblENTS
The authors wish to thank Dr A K. Slnha, Reader In Chemistry. College. Patna-SO0004 for his support during this investigation
B.
N.
FCEFEFZENCES
1 33
A I KIPRIWOL and (1950). Chew Absr I K USHENKO Ukr I K USHLYKO CJhr
I K UsHErwho Izrar Al.ad NauL USSR . Ord Khml 35. 3265 (1951) k’l;m 211 . 20, 3SI (1954). Chem Absr . 50, 6019 (1956) AIhrm 211 21, 73s (1935). Chetn Absr , 50, 16752 (1956)
Nattk.
192
4 5. 6 7. 8 9 10 11 12 13 1-I 15. 16
I G FAFZBEN. Bnt Pat 495. 012 A I KIPFUANOV and I. K USHENKO. J Gem Chem US S R , 20, 514, Enghsh translation, 543 (1950) F. M TIER. J. Chem Sot, 1480 (1956) F. M HAMER. Cvanine dves and related comuounds New York. InterscIence Pubhshers Inc (1964) G~\es a ~omprehdnswe surxey of the subject covered by this paper W H. Mrus and J L B SMITH. J Chem Sot , 121, 2724 (1922) N P BHATTACHARYA and S N SANYAL. J. Indian Chem JCB ANEIUI. K. D. B-, Sot. 45, 496 (1968). J C Band S N. SANYAL. lndzan J Chem . 6. 346 (1968) S N. SSCNYAI_ Ph D. Thesis. Bihar Unwersny. India. p 103 (1966) R C SHAH. R. K DE~HPANDE’I and J S CMUBAI_. J Chem Sot. 645 (1933 J R J~H&OFI and R ADAMS. J Amer Chem Sot, 43, 2257 (1921) W H Mrus and W. Z POPE. J C/rem Sot , 121, 946 (1922) 0 DOEBNER and W V Mw, Chem Ser. 16. 2468 (1883) R J N SAMY. A K S~NHA and J C BANERJI _I Indian Chem SOC, 43. 255 (1966)
and Rz%=cr~s
Research
Substituted
1 (1980)
161-16,
Note
Benzylidene Cyanides B-N
Depamnent
of Chemrstry,S.P Dumka
JHA (Bhagalpur
College
(S P)-814101.
Unzuersl@),
Bthar, Indta
and J CBANEIRJI Dcpamnent
of Chemlshy, B N College. Puma Puma-800004, Bzhar. Kndla
Unwers~ry,
SUMMARY Eight new condensing
chain substttuted benzylidene cyanine 4-dimethylamino-2’-nitrobenzophenone
dyes and
have been prepared 4-drmethylamzno-3’S’-
by
dmitrobenzophenone with methiodides of quinaldine and 6_haloquinaldines, m absolute ethanol, using pipen’dine as a basic catalyst. The optical absorption and extra sensltisation data of the dyes have been recorded and compared with those of their methin analogues. The dyes absorb at longer wavelengths than thezr unsubstituted analogues, contrary to earlier observations.‘d The dyes obtained from the 2’-nitroketone are good sensitisers, whereas those obtained from the 3’,5’-dinitroketone, are densensitisers
1.
tN-l-R3DUCTION
Although quite a large number of 4-dialkylamino styryl dyes, containing different variously substituted heterocyclic nuclei are reported, and the effect on optlcal absorption and sensitisation of substituents in the hetero part of ‘rhe hemicyanines has been extensively studied,’ very little work has been carried out to study the effect of substituents in the methin chain of the dye Moreover, Q!- and p-methin substitutions in styryl cyanines are mo1ecules.8-” reported to cause a hypsochromic shift in the absorption maxima, when but the extent of the hypsocompared to their unsubstituted analogues,‘-3 chromic shift is less pronounced in the case of P-substituted products.It was 161 ~ye_~and figments England, 1980 Printed an Nor&em
0143-7208/80/0001~161/$02-25-_0 Ireland
Apphed
Science Publishers
Ltd,
162
B
N JHA
J CBANEtRIl
therefore of interest to prepare some ,G-methin substituted styryi cyanines and study thetr opttcal properties systematically_ The p-methtn chain substitution can be effected by using suitable I-pdtalkylamino ketones in place of 4-p-dialkylaminoaldehydes This paper reports the preparation of dyes denved from two ketones, 44-dimethylamtno-3’.5’-dmitrodimethylamino-2’-nitrobenzophenone and benzophenone. whtch were obtained by the method of Shah er al.” with suttable modificattons. The quatemtsed bases required, were prepared by heating the base with methy iodide-l3 The synthesised ketones were separately condensed rn the usual waylJ wtth methtodtdes of qutnaldine” and 6-chloro-. 6-bromoand 6-iodoqutnaldinest3 I6 tn absolute ethanol in the presence of a few drops of ptperidtne to afford etght new dyes (II),,-D2,) as in Scheme 1 The dyes (D,,-D,,) obtained from 4-dtmethylamtno-2’-nttrobenzophenone from 4-dimethylamtno-3’.5’-dinttrobenzophenone are and dyes (D3, -DZ2) htghly crystalline and are mostly dark vrolet m colour. Then- alcoholtc soluttons are either reddish vtolet or violet The colour is reverstbtly dtscharged by addttion of mtneral actds and regenerated on bastficatton, indtcsttve of the charactensttc of cyantne dyes ,!3-Methrn substttutton may affect the resonance stabiltsatron of substttuted dye molecules stertcally and electrontcally. as the substituents under study are electron attracttng. The stenc htndrance to resonance tn the matn conjugated chatn due to bulkrness of the substttuents IS hkely to be significant too. The data for optical absorptton maxima and the ranges of extra sensttisation have been recorded. analysed and compared wtth those of their corresponding styryl analogues wherever posstble and reasonable conclusions have been drawn.
2
covcJ-us10ss
The absorptton ma\tma and extra senstttsatton of the newly prepared dyes and those of thetr styryl analogues. available tn the literature. are shown tn Table 1 for comparison. It ~111 be evident from the absot-ptton data that P-methtn substttutton, whether by 2-nttrophenyl or by 3.5-dtnitrophenyl, has caused an almost untform bathochromtc shift in A,,, by about 30 rnp. It will also be seen that 6-substttution of the heteronucleus has caused only a slight bathochromic shift the order being 6-H < 6-CI < 6-Br < 6-I tn both the 2-nitro senes and tn A,,. the 3.5dmicro sertes Analysts of the sensittsation data. however, does not lead to any definite generalisation The p-2-nitrophenyl dyes are inferior sensitisers to their unsuhstttuted analogues. while the P-3.5-dtmtrophenyl dyes are desensittsers
163
164
BNJHAJCBANEFUI 1
TABLE THE RECORDED
DATA
OF
ABSORPTION DYES
BENZYUDENECYANlNE
M/U5MA
AND
-l-HOSE
D,, D,, D 2” D,, D 71 Dh D 14
578 579 583 569 578 580 583
620 dc, 630 630 650 Da Da D” Da
w. lbvr nu, c rm. c I, Ic
ECl-R4
SENSll-ISAl-ION TITRYL
OF
THE
ANALOGUES
Exfra
sensNzsatzon
klU.S (mw)
range her)
560
530
680
580
11
590 u 590 590 -
548 550 552 530 548 550 552
650 650 650 680 650 650 650
595 595 600 580 595 595 600
16 16 16 11 16 16 16
(mw)
56.4
AND
IJN-
sensrfrsanon
range
D,,
OF
Unsubshtuted styryl dyes Cfrom rhe Lferufure)
Subsntured benzylrdene cyanme dyes Extra
(h,,)
Reference
c connected. I Intense, u unpronounced. w weak, dc &sconnected. Ic loosely connected, ml moderately Intense lbvr Intense In blue-violet range, D desenslt,ser a In all cases, lntenslty m blue-violet range IS decreased The desenslhsmg properry vanes En the order D,,CD,,
3.
ECXPEFUhfJ3J-l-AL
3.1. TIze ketones For the preparation of ketones, the general method amrnobenzophenones and therr substituted products adopted wrth some procedural modifications.
of production of alkylby Shah et al.” was
(I) 4-Dimethylamino-2’-mtrobenzophenone: Dtmethylanihne (8 ml) was added in portions to a mixture of o-nitrobenzanihde (3g) and phosphorus oxychloride (8 ml) and warmed (4045°C) for 8 h. The viscous mass, on extracting with hydrochlonc acid, was almost neutralised with sodium hydroxide solution and rendered homogeneous with alcohol. The ketone, which separated after additton of a few drops more of sodium hydroxtde solution and chilling, was recrystallised from toluene as shining deep orange leaflets (yield 30%. m p. 24%50°C; ref. 12. yield not mentioned, m-p. 251-53°C). (ii) 4-Dimethylamlno-3’,5’-dmltrobenzophenone: 3,5-Dinitrobenzanilide (5 g) and dimethylanihne (7 ml) were mixed together and phosphorus oxychloride (7 ml) was slowly added. The mixture was heated on a steam bath for
6-Iodoquumldtne
Qumaldmc
6Chloroqumaldme
G-Bromoquinaldmc
6-lodoqmnaldmc
D *,,
D,,
D 22
D 21
D zJ
2-p-Dlmetllylamlno(p-2mtrophenyl)styryl qumohne 2-p-Dlmethylamino(/.S2nrrorphenyl) sty1 y&6chloroqumohnc 2-p-Dlmethylammo(p-2. mtrophcnyl) slyryl-6bromoqumohnc 2-p-D~me~hylammo(/3-2. mlrophenyl) slyryl-6~odoqumohne 2-p-Drmcthylannno(p-3,5dmnrophyenyl) styrylqmnolmc 2-p-Dlmethylammo(p-3,5dmrlrophcnyl) styryl6-chloroqumohnc 2-p-Dlmcthylanlmo(p-3,5dmrtrophcnyl) styryl6.bromoqumohnc 2-p-Drmethylammo(p-3,5dmdrophcnyl! styryl-6rodoquinolme dvc wgr
dvc wrl
dv IC wrr
dv IC
dv VI wbr
WTT
dv sn
dv +n wrt
dv IC
CpNal calaur and s/mpP
75
73
71
67
37
41
58
61
Meld (%I
161
231
208
(“Cl
Mp
WIIII
Molecular formula
DENZYLlD@NE CYANIMZ DYES
’ dv dark vlolei, sn small needles, tc tmy crystals, dvc dark violet crystals, wbr wnh blue rellcx, wgr wrr w1t11 red rcflcx, wrl wnh rcddrsh tmgc
6-Bromoqurnakhne
6Chloroqumaldme
Qurnnldmc
Method& of base used
DW
Dul
47
Dye symbol
TABLE 2 ANALYI’ICAL DATA OF THE SUBSTK~J
35.83
33-84
26~31
21-78
38 34
33.58 2841
23~61
7.91
8.4;’
9.08
9462
6.33
6.82 7 35
I.82
35.88
33.88
26 35
21.82
38.31
33 62 28.45
2365
green rcflcx, wrl with rcddlsh IusIrc,
7.86
8.42
9 01
9 51
6 21
6.11 129
I*11
Hal
N
N
Hal
Calc (X)
Fourrd(%)
a
#
1
I m
$
166
B
N .JHA,J
C BANERJl
6 h and then on an oil bath (115-120°C) for a further 4 h. The acid extract of the crude product was neutralised with sodium hydroxide solution and the separated ketone recrystallised from a mixed solvent, ethanol: benzene (3: l), as light orange coloured shining woolly crystals, (yield 40%, m-p. 193-94°C). C,sH,,NL& 3.2.
Found: requires:
Tile quaternary
C, 57-11; H. 4-06; C. 57- 14: H, 4-14:
quinaldmlum
N. 13-28% N, 13.33%
salts
salts were obtamed by adoptmg the general method of preparation of Johnson and Adams.‘3 The bases and methyl iodide (1: l-5 M) were heated In a pressure bottle on a steam bath for 24 h and the product recrystallised from hot water. The
3 3.
quaternised
The
benzyhdene
cyatlrne
dyes
A nuxture, contaming requlslte amounts of the ketone, the quatemary salt. ethanol and a few drops of piperidlne was refluxed mildly under a moisture trap for about 2 h The resulting solution. on cooling. afforded the dye. which was recrystalllsed from methanol The percentage analysis. yield. m p (uncorrected). etc of the dyes are given In Table 2 3.-I Recordttlg of opucal properrres The absorption maxlma of the dyes were recorded on an Beckmann Spectrophotomerer. Model DU In l/1000 ethanolic solutions. The sensitlsatlon spectra were recorded on an Adam Hllger Wedge Spectrograph on Ilford N40 process plates, bathed In dilute ethanol (1 _3) solutions (l/50 000) of dyes. The plates after -t min bathing were dried. exposed for 4 mm to light from a 150 c-p point-o-hte lamp
AChNOWLEDGEblENTS
The authors wish to thank Dr A K. Slnha, Reader In Chemistry. College. Patna-SO0004 for his support during this investigation
B.
N.
FCEFEFZENCES
1 33
A I KIPRIWOL and (1950). Chew Absr I K USHENKO Ukr I K USHLYKO CJhr
I K UsHErwho Izrar Al.ad NauL USSR . Ord Khml 35. 3265 (1951) k’l;m 211 . 20, 3SI (1954). Chem Absr . 50, 6019 (1956) AIhrm 211 21, 73s (1935). Chetn Absr , 50, 16752 (1956)
Nattk.
192
4 5. 6 7. 8 9 10 11 12 13 1-I 15. 16
I G FAFZBEN. Bnt Pat 495. 012 A I KIPFUANOV and I. K USHENKO. J Gem Chem US S R , 20, 514, Enghsh translation, 543 (1950) F. M TIER. J. Chem Sot, 1480 (1956) F. M HAMER. Cvanine dves and related comuounds New York. InterscIence Pubhshers Inc (1964) G~\es a ~omprehdnswe surxey of the subject covered by this paper W H. Mrus and J L B SMITH. J Chem Sot , 121, 2724 (1922) N P BHATTACHARYA and S N SANYAL. J. Indian Chem JCB ANEIUI. K. D. B-, Sot. 45, 496 (1968). J C Band S N. SANYAL. lndzan J Chem . 6. 346 (1968) S N. SSCNYAI_ Ph D. Thesis. Bihar Unwersny. India. p 103 (1966) R C SHAH. R. K DE~HPANDE’I and J S CMUBAI_. J Chem Sot. 645 (1933 J R J~H&OFI and R ADAMS. J Amer Chem Sot, 43, 2257 (1921) W H Mrus and W. Z POPE. J C/rem Sot , 121, 946 (1922) 0 DOEBNER and W V Mw, Chem Ser. 16. 2468 (1883) R J N SAMY. A K S~NHA and J C BANERJI _I Indian Chem SOC, 43. 255 (1966)