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Studies on ylides: generation and reactions of new 2-naphthylmethylenetriphenylarsenanes
-:
-.
175
Journal of O&anometabic Chemisfry,IO8 (1976) 175~181 @ Elsevi&SequoiaSk, Laus+ne - Printedin The Net&xlands
S+UDIES ON YLIDES: GENERATION&ND REACTIONS OF NEW 2-NAPHTHYLM ETHYLENRTRIPHENYLARSENANES
PURSHOTTAM
S. KENDURKAR
and RAM S. TEWARI
*
Department of Chemistry, Harcourt Butler Technological Institute, Kanpur-208002
(India)
(Received October 17th, 1975)
Two new semistabilized arsonium ylides have been generated and treated with carbonyl compounds. In reaction with carbonyl compounds, the carbanionic centres of both the ylides attack the carbonyl carbon to form similar cyclic intermediates. These intermediates, however, decompose to give different reaction products. The structures of the products are indicated by IR and NMR spectroscopy.
Introduction Recently studies of the structural factors which influence the course of olefination or epoxidation of cyclic transitional intermediate I in reactions of semistabilized arsonium ylides with carbonyl compounds have been reported Ph,As
CHR
I
I
0
CHAr
(I) [l-4]; We now describe studies on the interesting-behaviour of 2-naphthylmethylene@iphenylaenanes, a new series of arsonium ylides, towards carbonyl compounds,
._
.:
.,
._
and discussion
Restiti
:
*
Treaiment of triphenylarsine with 2-bromomethylnapthalene and l-brtinio2-brotiomethylnaphthalene.at elevated tempemtures affordsd Z-naphthylmethyl~i~hen~~~soniurn bromide (Da) and l-bromo-Z-naphthylmethyl~iphenyl~soniuqx bromide (XIb) in good yields. Transient intense yellow colorations indieated the generation ,of 2-na~hthy~ethylene~iphenyl~se~ne (IIIa) and I-bromo2-naphthy~ethylen~~ipheny~sen~e (IIfb), which results from proton abstraction from their respective salts (IIa and IIb) with sodium hydride in benzene (Scheme 1). The structural identity of the new arson&n ylides (II&, IIfb) SCHEME
1
(IIa)
R’ =
H
(Eta)
R’
(IIb)
R’ =
Br
fmbl
R’ =
=
Er
+Al-*CHO
R’
CH-CH Pi%+
H
* Ar
-
Path
I
E
I
+
I (IPa)
R’=
H;Ar
zGHs
(IfLb)
R” =
H ;Ar
=
UJZc)
R
H ;Ar
I
4-CH30C&
(IEd)
R’ =
H
=
4-CICBH4
(EZe)
R’ =
H ; At
=
2-N92CsH,
=
; AT-
Path
A
4-CH3C+& CH=CH-
Ar
R’z
Br;Ar
Ceb)
R’ =
Br;
Ar
(SC>
R’ =
Er;
AS- z.z 4-CHJOC&~
(Pd)
R’
=
Br;
At-
=
?.4-tOCH201f&Hj
WeI
R’ =
Br;
Ar
=
451%X4
fPf)
R’=
Er;Ar
s
2.4-
c.?g)
R’
=
BrjAr
=
4--No&$‘&
tPh>
R‘
=
6r:Ar
Br;
3-Cff.&t-i~
- CCH,Otz-
ze
3.4
Ar
=
2-pyridyt
=
S-anthryl
(Pjt
R’
=
E3r; Ar
Cnr)
R’
=
a~-;
EIT)R’=
CT&
=
PhgASC
EiXl
(Pi 1 R’ =
=
+
Arm_=
Br ; ArCH
6--BrC$fz
9-fiuorenyf =
9-anthryl
was cunfirxned by NMR spectra of their corresponding salts (IIa, IIb) and by ~e~,~be~c~ reactions. The ylide IIIb followed a similar course of reaction (Path A) towards c~~bonyl, compounds as reported for the-analogous Z-~phthylmetbylen~~iphe~ylphosphors ylide [ 51..IIowever, ylide IIIa followed a different path B. ~eem~gly, the ~b~oni~ centres of both ylides (IIIa, IIIb) attack the carbonyl -. ._
‘.. ,:. ..;-
I
:
‘..
177 carbon to form similar cyclic intermediates (I) which decomposed via path A or path B to give different reaction products (Scheme 1). Thus, the yhde II& reacted with a range ‘of substituted benzaldehydes at room temperature, following path B, to give epoxides (IVa-IVe) in good yields, whereas the reaction of ylide IIIb with a series of aromatic aldehydes under similar reaction conditions followed exclusively olefination (path A) affording the olefins (Va-Vj) (Scheme 1). Similarly, the reaction of ylide IIIb with 9-fluorenone and 9-anthrone was also successful at elevated temperature to give exocyclic olefins (VI and VII) in fair yields. With carbonyl compounds the ylide IIIa gave epoxides exclusively but ylide IIIh gave only olefins. In no case were both olefins and epoxides isolated and !, in all cases only trans-epoxides or truns-olefins were detected_ All the epoxides (IVa-IVe) (Table 1) and olefins (Va-Vj, VI and VII) (Table 2) obtained in this study are new. Their structures were confirmed by IR and NMR spectral studies (Table 3). IR spectra of the ethylene epoxides showed two characteristic absorption bands near 832 and 848 cm-’ ; the latter absorption bands are attributed to the asymmetrical ring stretching of the C-C bond due to contraction of the C-C bond. The NMR spectra of ethylene epoxide showed a characteristic absorption of epoxy protons, -CH\*/cH-P at 6 3.96-4.26 ppm and an aromatic multiplet in the range of 6 6.77-8.03 ppmThe IR spectra of trans-ethylenes (Va-Vj) showed absorptions at 1635-1605 (v(C=C)) and at 987-950 cm-‘. The latter absorptions are associated with outof-plane deformations of hydrogen attached to the trans-olefinic system [6]. The NMR spectra of ethylenes exhibited olefinic proton resonances in the range 6 6.75-7.18 ppm and aromatic multiplet resonances in the range 6 6.90-8.30, ppm. The methylene protons in the exocyclic olefin VII absorbed at 6 1.29 ppm. TABLE
1
trans-DIARYGSUBSTITUTED
EPOXIDES
QJQJC~TH-A~
Cornpound
Ax
Yield W)
Recast. sowent
M.P. (“Cl
Empirical formula
IVa
CsHs
so
EtOH
113-115
C1sH140
IVb
.4CH3C6Ef4
80
EtOAc
110-112
C19H160
IVC
4CH30C6H4
85
CHC13/MeOH
x39--140
C19H1602
IVd
4CICsH4
92
C6H6/hexane
128-130
C1sH13CC1
IVe
2-NC$&Hq
95
EtOAc
122-123
CISkl3NO3
. -.
Analysis Found (cald.)
C
I-I
87.77 (87.79) 87.67 (87.68) 82.62 (82.65) 77.01 <77.00) 74.22 (74.23)
5.68 (6.69) 5.13 (5.15) 5.79 (6.79) 4.62 (4.63) 4.44 (4.46)
-
‘.
‘/
”
C6HS
vo
‘(
_
’ Py e pyridyl, Ai = nnthryl, Fl = fluorenyl,
:ArCH=9-An
9-Anthryl’
v
VII
2-Py a
Vi
ArCH=g.Fl
8,4-(CH30)2.6.BrC6H2
Vh
VI
96
4-NC&jHq
Ve
40
60
69
60
60
70
2.4(Ci)$fjH3
76
70
60
62
66
_ -
Yield (%)
Vi
‘.
3,4-(CCH+)&,H3
Vd
4C1C6H4
4.OCH3CgH4
vc
,’ Ve ,.’
a-CH3CgH4
Ar
Vb
”
Ar
Compound
CH=CH-
--
tranr+DIARYL SUBSTITUTED OLEFINS (Vo-Vj, VI and VII)
TABLE 2
..,
-
EtOH (90%) CHCl$hexane
EtOH/H20 (3:l) Et011 (90%) EtOH
CHClg/hexane
CHCl#exane
EtOH
EtOH
EtOH
C~H~/hexane
CHClaihexane
Recryst. solvent
108-110
102
166-167
144-146
178-180
168-160
139-140
141
118-120
130-136
88-90
112-116
M.P. (OC)
_
-
C2sHt7Br
CwHtsBr
CsH17Br
Ct7H12NBr
C2oH I aBY&
-
C18HtzNQBr
CtaHItBrC12
CI$112BrCI
Ct9Ht3BrC2
CI~HISB~C
Ci9HisBr
CISHI~B~
Empirical formula
-
-
--
69.87 (69.90) 70.66 (70.68) 67024 (67.26) 64.29 (64.30) 62.94 (62.96) 67.13 (67.14) 61.03 (61.08) 66.77 (66.80) 66.79 (66.80) 76.26 (76.28) 76.18 (76.19) 76.66 (7G.66)
C
4.18 (4,20) 4.63 (4.84) 4.41 (4.42) a.66 (3.67)’ 3.61 (8.60) 2.90 (2.92) a.36 (3.38) 3.66 (3,67) 3.86 (3.87) 4.14 (4.16) 3.90 (3.91) 4,28 (4.28)
H
:’
Analysis Found (c&d,) (%)
,’
2
Y
”
179 TABLE
3 SPECTRA
NMR
(CDCX3)
OF EPOXIDES
AND Number protons
Compound
6 @pm)
IVa
7.31-8.02. 4.12. q.
m a
12H 2H
IVb
7.00-7.95. 3.97. q
m
11H 2H
dLEFINS Assignment
of
Aromatic ““vCHAromatic -CHvcH-
2.36. s 6.77-8.04. 3.96. q
WC
m
-
3.32. s 7.10-8.03.
SVd
3H 11H 2H
m
3.98. q 7.08-8.28, 4.26. q
m
11H 2H
Va
7.28-8.05, 6.95. q 7.32-8.00. 6.99. q 2.81, s 7.50-7.90. 6.98. q 3.60. s 7.40-6.20. 7.00. q 6.10, s 7.42-8.30. 7.18. q 7.30-8.20. 6.82. q 4.05. s 6.90-8.10. 6.75. q 7.50-8.01, 7.33, s 1.29, s
m
11H 2H 10H 2H 3H 10H 2H 3H SH 2H 2H 10H 2H 8H 2H 6H 15H 2H 14H 1H 2H
VC
Vd
VIZ vb
vj VII
a m. multiplet:
s. singlet;
m
m
m
m m
m m
Aromatic -CHvcHOCH3 Aromatic
3H 11H 2H
IVe
vb
CH3
-CH~O~cHAromatic “HvCHAromatic -CH=CHAromatic -CH=CHC*3 Aromatic -CH-CH-0CH3 Aromatic -CH-H-OCHzOAromatic -CH=CHAromatic -CH=CHOCH3 Aromatic -CH==CHAromatic ;C==CH;CH2
9. quartet.
Experimental Melting p&h were determined on a .Gallenkamp apparatus and are uncorrecti tid. IR spectra (KBr) were recorded on a Perkin--Elmer infracord instrument. NMR-speck-were recorded (CDC13.solutiops) on a Varian A6@ iptitrdm&er using PS qs &i titer@ stahdard and are reported in S (ppm)‘valu&..-All products Were_sep&atid.qd ph%!ied.by. c@umn cbr&atogra& using al@mti~& _puritjr_ l&&sce+&i .ey.TM=. ; .: ._ _ : -. .- ; : y -1. : : ... ; -’
;-I
.. __ -: -._: :-.
.....
.; ;
:. -. .. : : ,.. _... : : :. ‘__~ -._ ; .. _.__,-1. _’ .:
.. ..-
.- ...
-. .
&&ar&iori of 2-naphthylmkthyltriphenylarsonium br&nide (Ila) .. A mixtie of triphenylarsme (12.2 g, 0.04 mol) and &bromomethylnaphthalene (9.6 g, 0.044 mol) wak heated-as a melt at 100°C for -60 h. The i_esult&g solid.was washed with ether and.extracted with chloroform. The excess of solvent was evaporated under reduced pressure and n-hexarie was added to precipitate 8.4 g (40%) of 2-naphthylmethyltriphenylarsonium bromide (Da). An analytical sample of salt (IIa) was recrystallized twice from chloroform/nhexane to give white microcrystals, m-p. 158°C. NMR spectrum (CDC13): S (ppm) 7.42-7.84 (22H, aromatic protons, multipiet) and 5.68 (2H, methylene protons, singlet). (Found: C, 66.00; H, 4.52. CZ9H,,AsBr calcd.: C, 66.03; H, 4.55%). Preparation of I-bromo-Z-naphthylmethyltriphenylarsonium bromide (IIb) A solution of 12.2 g (0.04 mol).of triphenylarsine and 13.2 g (0.044 mol) of 1-bromo-2-brtimomethylnaphthalene in 60 ml of anhydrous benzene was boiled under reflux for 6 days in an inert atmosphere of nitrogen. Excess of solvent was evaporated off on a steam bath and petroleum ether (60-80”) was added to precipitate 8 g (32%) of 1-bromo-2-naphthyhnethyltriphenylarsonium bromide (IIb). The salt IIb was recrystallized three times to give grey-white microcrystals, m-p. 148-150°C. NMR spectrum (CDC13): 6 (ppm) 7.41-7.92 (21H, aromatic protons, multiplet) and 5.84 (2H, methylene protons, singlet). (Found: C, 57.41; H, 3.75. C29H2&sBr calcd.: C, 57.42; H, 3.79%). Reaction’of ylide I_& with benzaldehydes To an intense yellow suspension of ylide IIIa, generated from 2.1 g (0.004 mol) of salt IIa and 0.5 g (50% slurry) of sodium hydride in 60 ml of anhydrous benzene, was added, under nitrogen, 0.004 mol of substituted benzaldehyde. The mixture was stirred at room temperature for 3 days after which it was poured into water. The benzene layer was washed with water, dried and evaporated. The residue was chromatographed on neutral alumina. Elution with petroleum ether (40-60”) gave triphenylarsine, m-p. and mixed m-p. 60°C. Elution with petroleum ether (40--60”)/benzene (1:l) gave I-aryl-2-(2-naphthyl)-1,2-ethylene epoxide (IVa-IVe) in fair to good yields_ It was further purified by crystallization from appropriate solvent (Table 1). Reaction of yiide IIfi with aromatic aldehydes To a stirred suspension of ylide DIb, prepared Erom 2.4 g (0.004 mol) of salt IIb and 0.5 g (50% slurry) of sodium hydride in 100 ml of anhydrous benzene, was added, under nitrogen, 0.004 mol of aromatic aldehyde. The reaction proceeded at room temperature for 24 h. The resulting precipitate, conkiining triphenylarsine oxide and unreacted sodium hydride, was removed by filtration and the filtrate was evaporated under reduced pressure. The oily product ‘was chromatographed over neutral.alumina. Elution with benzene gave frans-l-aryl-2-(1-bromo-2naphthyl)ethylene (Va-Vj) in fair to good yield.. It was furt&r~~~%ed by recrystallization from an appropriate solvent (Table 2). Reaction of @de III@ ‘&ith,exocyclic ketones : To a suspension of ylide I&, prepared from 2.4 g (0.004 mol)
-
of
salt Ilh and
T
,181
.0;5 g (50% slurry) of sodium hydride in 100 ml of anhydrous benzene under
nitrogen, was added 0.004 mol of -exocyClic ketone. -The reaction mixture was heated under reflux for 3 days. The resulting -solid; &ontaining unreacted sodium hyd&de and triphenylarsine oxide, was’kemoved and the filtrate was ebncent+ted on a stG.m bath under reduced pressure. The resulting oily mass was chroma-
.tographed over-alumina. Elution with benzene afforded exocyclic olefin (VI and VII) in fair yield (Table 2). Acknowledgements The authors thank Dr. SD. Shukla, Director, H.B. Technological Institute, Kanpur-2 (India), for providing facilities. One of the authors (P&K.) thanks C.S.I.R., New Delhi, for the award of Post Dot. Fellowship. References 1 2 3 4 5 6
S. Trippett and M.A. Walker. J. Chem. Sot. C. (1971) 1114. P.S. Kendurkar and R.S. Tewari. J. Organometal. Chem.. 60 (1973) 247. P.S. Kendurkar and R.S. Tewaxi. J. Organometal. Chem.. 85 (1975) 173. N. Kumari. P.S. Kendurkarand R.S. Tewari, J. Organometal. Chem.. 96 (1975) 237. J-P. Greets and R.H. Martin, Bull. Sot. Chim. Beiges. 69 (1960) 563; Chem. Abstr.. 55 (1961) L.J. Bellamy. The Infrared Spectra of Complex Molecules. Wiley. New York. 1954. p_ 31.
14410~.
:
; . :
:.
-.
175
Journal of O&anometabic Chemisfry,IO8 (1976) 175~181 @ Elsevi&SequoiaSk, Laus+ne - Printedin The Net&xlands
S+UDIES ON YLIDES: GENERATION&ND REACTIONS OF NEW 2-NAPHTHYLM ETHYLENRTRIPHENYLARSENANES
PURSHOTTAM
S. KENDURKAR
and RAM S. TEWARI
*
Department of Chemistry, Harcourt Butler Technological Institute, Kanpur-208002
(India)
(Received October 17th, 1975)
Two new semistabilized arsonium ylides have been generated and treated with carbonyl compounds. In reaction with carbonyl compounds, the carbanionic centres of both the ylides attack the carbonyl carbon to form similar cyclic intermediates. These intermediates, however, decompose to give different reaction products. The structures of the products are indicated by IR and NMR spectroscopy.
Introduction Recently studies of the structural factors which influence the course of olefination or epoxidation of cyclic transitional intermediate I in reactions of semistabilized arsonium ylides with carbonyl compounds have been reported Ph,As
CHR
I
I
0
CHAr
(I) [l-4]; We now describe studies on the interesting-behaviour of 2-naphthylmethylene@iphenylaenanes, a new series of arsonium ylides, towards carbonyl compounds,
._
.:
.,
._
and discussion
Restiti
:
*
Treaiment of triphenylarsine with 2-bromomethylnapthalene and l-brtinio2-brotiomethylnaphthalene.at elevated tempemtures affordsd Z-naphthylmethyl~i~hen~~~soniurn bromide (Da) and l-bromo-Z-naphthylmethyl~iphenyl~soniuqx bromide (XIb) in good yields. Transient intense yellow colorations indieated the generation ,of 2-na~hthy~ethylene~iphenyl~se~ne (IIIa) and I-bromo2-naphthy~ethylen~~ipheny~sen~e (IIfb), which results from proton abstraction from their respective salts (IIa and IIb) with sodium hydride in benzene (Scheme 1). The structural identity of the new arson&n ylides (II&, IIfb) SCHEME
1
(IIa)
R’ =
H
(Eta)
R’
(IIb)
R’ =
Br
fmbl
R’ =
=
Er
+Al-*CHO
R’
CH-CH Pi%+
H
* Ar
-
Path
I
E
I
+
I (IPa)
R’=
H;Ar
zGHs
(IfLb)
R” =
H ;Ar
=
UJZc)
R
H ;Ar
I
4-CH30C&
(IEd)
R’ =
H
=
4-CICBH4
(EZe)
R’ =
H ; At
=
2-N92CsH,
=
; AT-
Path
A
4-CH3C+& CH=CH-
Ar
R’z
Br;Ar
Ceb)
R’ =
Br;
Ar
(SC>
R’ =
Er;
AS- z.z 4-CHJOC&~
(Pd)
R’
=
Br;
At-
=
?.4-tOCH201f&Hj
WeI
R’ =
Br;
Ar
=
451%X4
fPf)
R’=
Er;Ar
s
2.4-
c.?g)
R’
=
BrjAr
=
4--No&$‘&
tPh>
R‘
=
6r:Ar
Br;
3-Cff.&t-i~
- CCH,Otz-
ze
3.4
Ar
=
2-pyridyt
=
S-anthryl
(Pjt
R’
=
E3r; Ar
Cnr)
R’
=
a~-;
EIT)R’=
CT&
=
PhgASC
EiXl
(Pi 1 R’ =
=
+
Arm_=
Br ; ArCH
6--BrC$fz
9-fiuorenyf =
9-anthryl
was cunfirxned by NMR spectra of their corresponding salts (IIa, IIb) and by ~e~,~be~c~ reactions. The ylide IIIb followed a similar course of reaction (Path A) towards c~~bonyl, compounds as reported for the-analogous Z-~phthylmetbylen~~iphe~ylphosphors ylide [ 51..IIowever, ylide IIIa followed a different path B. ~eem~gly, the ~b~oni~ centres of both ylides (IIIa, IIIb) attack the carbonyl -. ._
‘.. ,:. ..;-
I
:
‘..
177 carbon to form similar cyclic intermediates (I) which decomposed via path A or path B to give different reaction products (Scheme 1). Thus, the yhde II& reacted with a range ‘of substituted benzaldehydes at room temperature, following path B, to give epoxides (IVa-IVe) in good yields, whereas the reaction of ylide IIIb with a series of aromatic aldehydes under similar reaction conditions followed exclusively olefination (path A) affording the olefins (Va-Vj) (Scheme 1). Similarly, the reaction of ylide IIIb with 9-fluorenone and 9-anthrone was also successful at elevated temperature to give exocyclic olefins (VI and VII) in fair yields. With carbonyl compounds the ylide IIIa gave epoxides exclusively but ylide IIIh gave only olefins. In no case were both olefins and epoxides isolated and !, in all cases only trans-epoxides or truns-olefins were detected_ All the epoxides (IVa-IVe) (Table 1) and olefins (Va-Vj, VI and VII) (Table 2) obtained in this study are new. Their structures were confirmed by IR and NMR spectral studies (Table 3). IR spectra of the ethylene epoxides showed two characteristic absorption bands near 832 and 848 cm-’ ; the latter absorption bands are attributed to the asymmetrical ring stretching of the C-C bond due to contraction of the C-C bond. The NMR spectra of ethylene epoxide showed a characteristic absorption of epoxy protons, -CH\*/cH-P at 6 3.96-4.26 ppm and an aromatic multiplet in the range of 6 6.77-8.03 ppmThe IR spectra of trans-ethylenes (Va-Vj) showed absorptions at 1635-1605 (v(C=C)) and at 987-950 cm-‘. The latter absorptions are associated with outof-plane deformations of hydrogen attached to the trans-olefinic system [6]. The NMR spectra of ethylenes exhibited olefinic proton resonances in the range 6 6.75-7.18 ppm and aromatic multiplet resonances in the range 6 6.90-8.30, ppm. The methylene protons in the exocyclic olefin VII absorbed at 6 1.29 ppm. TABLE
1
trans-DIARYGSUBSTITUTED
EPOXIDES
QJQJC~TH-A~
Cornpound
Ax
Yield W)
Recast. sowent
M.P. (“Cl
Empirical formula
IVa
CsHs
so
EtOH
113-115
C1sH140
IVb
.4CH3C6Ef4
80
EtOAc
110-112
C19H160
IVC
4CH30C6H4
85
CHC13/MeOH
x39--140
C19H1602
IVd
4CICsH4
92
C6H6/hexane
128-130
C1sH13CC1
IVe
2-NC$&Hq
95
EtOAc
122-123
CISkl3NO3
. -.
Analysis Found (cald.)
C
I-I
87.77 (87.79) 87.67 (87.68) 82.62 (82.65) 77.01 <77.00) 74.22 (74.23)
5.68 (6.69) 5.13 (5.15) 5.79 (6.79) 4.62 (4.63) 4.44 (4.46)
-
‘.
‘/
”
C6HS
vo
‘(
_
’ Py e pyridyl, Ai = nnthryl, Fl = fluorenyl,
:ArCH=9-An
9-Anthryl’
v
VII
2-Py a
Vi
ArCH=g.Fl
8,4-(CH30)2.6.BrC6H2
Vh
VI
96
4-NC&jHq
Ve
40
60
69
60
60
70
2.4(Ci)$fjH3
76
70
60
62
66
_ -
Yield (%)
Vi
‘.
3,4-(CCH+)&,H3
Vd
4C1C6H4
4.OCH3CgH4
vc
,’ Ve ,.’
a-CH3CgH4
Ar
Vb
”
Ar
Compound
CH=CH-
--
tranr+DIARYL SUBSTITUTED OLEFINS (Vo-Vj, VI and VII)
TABLE 2
..,
-
EtOH (90%) CHCl$hexane
EtOH/H20 (3:l) Et011 (90%) EtOH
CHClg/hexane
CHCl#exane
EtOH
EtOH
EtOH
C~H~/hexane
CHClaihexane
Recryst. solvent
108-110
102
166-167
144-146
178-180
168-160
139-140
141
118-120
130-136
88-90
112-116
M.P. (OC)
_
-
C2sHt7Br
CwHtsBr
CsH17Br
Ct7H12NBr
C2oH I aBY&
-
C18HtzNQBr
CtaHItBrC12
CI$112BrCI
Ct9Ht3BrC2
CI~HISB~C
Ci9HisBr
CISHI~B~
Empirical formula
-
-
--
69.87 (69.90) 70.66 (70.68) 67024 (67.26) 64.29 (64.30) 62.94 (62.96) 67.13 (67.14) 61.03 (61.08) 66.77 (66.80) 66.79 (66.80) 76.26 (76.28) 76.18 (76.19) 76.66 (7G.66)
C
4.18 (4,20) 4.63 (4.84) 4.41 (4.42) a.66 (3.67)’ 3.61 (8.60) 2.90 (2.92) a.36 (3.38) 3.66 (3,67) 3.86 (3.87) 4.14 (4.16) 3.90 (3.91) 4,28 (4.28)
H
:’
Analysis Found (c&d,) (%)
,’
2
Y
”
179 TABLE
3 SPECTRA
NMR
(CDCX3)
OF EPOXIDES
AND Number protons
Compound
6 @pm)
IVa
7.31-8.02. 4.12. q.
m a
12H 2H
IVb
7.00-7.95. 3.97. q
m
11H 2H
dLEFINS Assignment
of
Aromatic ““vCHAromatic -CHvcH-
2.36. s 6.77-8.04. 3.96. q
WC
m
-
3.32. s 7.10-8.03.
SVd
3H 11H 2H
m
3.98. q 7.08-8.28, 4.26. q
m
11H 2H
Va
7.28-8.05, 6.95. q 7.32-8.00. 6.99. q 2.81, s 7.50-7.90. 6.98. q 3.60. s 7.40-6.20. 7.00. q 6.10, s 7.42-8.30. 7.18. q 7.30-8.20. 6.82. q 4.05. s 6.90-8.10. 6.75. q 7.50-8.01, 7.33, s 1.29, s
m
11H 2H 10H 2H 3H 10H 2H 3H SH 2H 2H 10H 2H 8H 2H 6H 15H 2H 14H 1H 2H
VC
Vd
VIZ vb
vj VII
a m. multiplet:
s. singlet;
m
m
m
m m
m m
Aromatic -CHvcHOCH3 Aromatic
3H 11H 2H
IVe
vb
CH3
-CH~O~cHAromatic “HvCHAromatic -CH=CHAromatic -CH=CHC*3 Aromatic -CH-CH-0CH3 Aromatic -CH-H-OCHzOAromatic -CH=CHAromatic -CH=CHOCH3 Aromatic -CH==CHAromatic ;C==CH;CH2
9. quartet.
Experimental Melting p&h were determined on a .Gallenkamp apparatus and are uncorrecti tid. IR spectra (KBr) were recorded on a Perkin--Elmer infracord instrument. NMR-speck-were recorded (CDC13.solutiops) on a Varian A6@ iptitrdm&er using PS qs &i titer@ stahdard and are reported in S (ppm)‘valu&..-All products Were_sep&atid.qd ph%!ied.by. c@umn cbr&atogra& using al@mti~& _puritjr_ l&&sce+&i .ey.TM=. ; .: ._ _ : -. .- ; : y -1. : : ... ; -’
;-I
.. __ -: -._: :-.
.....
.; ;
:. -. .. : : ,.. _... : : :. ‘__~ -._ ; .. _.__,-1. _’ .:
.. ..-
.- ...
-. .
&&ar&iori of 2-naphthylmkthyltriphenylarsonium br&nide (Ila) .. A mixtie of triphenylarsme (12.2 g, 0.04 mol) and &bromomethylnaphthalene (9.6 g, 0.044 mol) wak heated-as a melt at 100°C for -60 h. The i_esult&g solid.was washed with ether and.extracted with chloroform. The excess of solvent was evaporated under reduced pressure and n-hexarie was added to precipitate 8.4 g (40%) of 2-naphthylmethyltriphenylarsonium bromide (Da). An analytical sample of salt (IIa) was recrystallized twice from chloroform/nhexane to give white microcrystals, m-p. 158°C. NMR spectrum (CDC13): S (ppm) 7.42-7.84 (22H, aromatic protons, multipiet) and 5.68 (2H, methylene protons, singlet). (Found: C, 66.00; H, 4.52. CZ9H,,AsBr calcd.: C, 66.03; H, 4.55%). Preparation of I-bromo-Z-naphthylmethyltriphenylarsonium bromide (IIb) A solution of 12.2 g (0.04 mol).of triphenylarsine and 13.2 g (0.044 mol) of 1-bromo-2-brtimomethylnaphthalene in 60 ml of anhydrous benzene was boiled under reflux for 6 days in an inert atmosphere of nitrogen. Excess of solvent was evaporated off on a steam bath and petroleum ether (60-80”) was added to precipitate 8 g (32%) of 1-bromo-2-naphthyhnethyltriphenylarsonium bromide (IIb). The salt IIb was recrystallized three times to give grey-white microcrystals, m-p. 148-150°C. NMR spectrum (CDC13): 6 (ppm) 7.41-7.92 (21H, aromatic protons, multiplet) and 5.84 (2H, methylene protons, singlet). (Found: C, 57.41; H, 3.75. C29H2&sBr calcd.: C, 57.42; H, 3.79%). Reaction’of ylide I_& with benzaldehydes To an intense yellow suspension of ylide IIIa, generated from 2.1 g (0.004 mol) of salt IIa and 0.5 g (50% slurry) of sodium hydride in 60 ml of anhydrous benzene, was added, under nitrogen, 0.004 mol of substituted benzaldehyde. The mixture was stirred at room temperature for 3 days after which it was poured into water. The benzene layer was washed with water, dried and evaporated. The residue was chromatographed on neutral alumina. Elution with petroleum ether (40-60”) gave triphenylarsine, m-p. and mixed m-p. 60°C. Elution with petroleum ether (40--60”)/benzene (1:l) gave I-aryl-2-(2-naphthyl)-1,2-ethylene epoxide (IVa-IVe) in fair to good yields_ It was further purified by crystallization from appropriate solvent (Table 1). Reaction of yiide IIfi with aromatic aldehydes To a stirred suspension of ylide DIb, prepared Erom 2.4 g (0.004 mol) of salt IIb and 0.5 g (50% slurry) of sodium hydride in 100 ml of anhydrous benzene, was added, under nitrogen, 0.004 mol of aromatic aldehyde. The reaction proceeded at room temperature for 24 h. The resulting precipitate, conkiining triphenylarsine oxide and unreacted sodium hydride, was removed by filtration and the filtrate was evaporated under reduced pressure. The oily product ‘was chromatographed over neutral.alumina. Elution with benzene gave frans-l-aryl-2-(1-bromo-2naphthyl)ethylene (Va-Vj) in fair to good yield.. It was furt&r~~~%ed by recrystallization from an appropriate solvent (Table 2). Reaction of @de III@ ‘&ith,exocyclic ketones : To a suspension of ylide I&, prepared from 2.4 g (0.004 mol)
-
of
salt Ilh and
T
,181
.0;5 g (50% slurry) of sodium hydride in 100 ml of anhydrous benzene under
nitrogen, was added 0.004 mol of -exocyClic ketone. -The reaction mixture was heated under reflux for 3 days. The resulting -solid; &ontaining unreacted sodium hyd&de and triphenylarsine oxide, was’kemoved and the filtrate was ebncent+ted on a stG.m bath under reduced pressure. The resulting oily mass was chroma-
.tographed over-alumina. Elution with benzene afforded exocyclic olefin (VI and VII) in fair yield (Table 2). Acknowledgements The authors thank Dr. SD. Shukla, Director, H.B. Technological Institute, Kanpur-2 (India), for providing facilities. One of the authors (P&K.) thanks C.S.I.R., New Delhi, for the award of Post Dot. Fellowship. References 1 2 3 4 5 6
S. Trippett and M.A. Walker. J. Chem. Sot. C. (1971) 1114. P.S. Kendurkar and R.S. Tewari. J. Organometal. Chem.. 60 (1973) 247. P.S. Kendurkar and R.S. Tewaxi. J. Organometal. Chem.. 85 (1975) 173. N. Kumari. P.S. Kendurkarand R.S. Tewari, J. Organometal. Chem.. 96 (1975) 237. J-P. Greets and R.H. Martin, Bull. Sot. Chim. Beiges. 69 (1960) 563; Chem. Abstr.. 55 (1961) L.J. Bellamy. The Infrared Spectra of Complex Molecules. Wiley. New York. 1954. p_ 31.
14410~.
:
; . :
:.