Reaction of spironaphthalenones with hydroxylamine: Part I. A reinvestigation of the mechanism

oo4o-4020/93 $5.00+.00 0 1993 Pagamon Press Ltd

Terrahedron Vol 49. No. 1, pp 113-124.1993 I’mted m Great Bnmn

Reaction of Spironaphthalenones with Bydroxylamine: A Reinvestigation of the Mecbanum

Part I.

* Tirumalai R. Kasturi , Srirangam K. Jayaram Palle V.P. Pragnacharyulu, Jitendra A. Sattigeri, Gowravaram M. Reddy and Kaipenchery A. Kumar

Department of Organic Chemistry Indian Institute of Science 560 012, INDIA. Bangalore

(Received in UK 27 August 1992)

hydroxylamine with lb-g on reaction Spironaphthalenones 6, 2b-g. Furanotropone the expected pyrrolotropones hydrochloride gave postulated as an intermediate in the formation of pyrrolotropones, remained unchanged on reaction with hydroxylamine hydrochloride in ethanol. Reaction the gave spironaphthalenones lh-o with NH20H.HCl of unsymmetrical 2h-o. rearranged pyrrolotropones

Abstract:

Abel

1

has

reported

'anhydro-oxime'

the

hydroxylamine

the formation in

the

on a few

investigated2

and

have

the cycloheptaindole

suggested They

compound.

have

also

through

the

(Scheme

11,

isolated

by them.

this

of

classical

a mechanism

intermediacy

has

been 3 et -- al this 2a for

compound

Dean

structure

for

formation

the

of furanotropone

with

la

transformations,

(pyrrolotropone)

suggested

designated

compound

spironaphthalenone

of

Structure

hydrochloride. based

of an anomalous

reaction

6

which

2a

of was

not

2,3-dichloro-5,6-dicyano-1,44 oxidation of the spironaphthalenone la by Kasturi -et al . is benzoquinone X-ray the furanotropone 6 and its structure was unambiguously confirmed by 3 If the mechanism proposed by Dean -et al. were crystal structure analysis. conditions to be correct, reaction of 6 with NH20H under similar reaction One

should

of

give

the compounds

with

It

obvious

furanotropone

NH20H,

yield;

starting

does

(Scheme

of la to 2a, but we,

for the formation

however,

material

the mechanism

6. The mechanism

for the conversion is enough

the

that

the

the

in

2a. However,

the pyrrolotropone

treated is

isolated

no reaction being

not

have

of pyrrolotropone

reaction

takes

113

found6

two moles

that

2a from

a longer

intermediacy

the

requires

time.

when

6 was

quantitatively5.

recovered

involve

1) also

occurred

one

mole

la in almost In

view

of

of NH20H

of NH20H the of

same these

114

T. R. KASTURIet al.

findings, an alternative mechanism

had to be visualised

for

this

reaction

and work was initiated in this direction.

r

6

11’ -

0

8

\ NH

’ /\ Za

Scheme

1

As a first step in our investigation,

it was necessary

to confirm

from structure of 2a. The only information that could be obtained 1 H NMR, which exhibited signals in the aromatic region,was the presence a

vinylic

C-proton

of an enone system [66.97

(d, J = 12.3 Hz)] and a

the its of NH

115

Reaction of spironaphthalenoneswith hydroxylamine-I

group

l612.97

13

(8,

c NMR could not D20 exchangeable)]. A reasonably good be obtained due to its high insolubility. However, X-ray crystal structure analysis (Fig.1) confirmed beyond doubt the structure proposed by Dean 3 et al . --

In order to establish the generality, it was necessary to study this reaction using a variety of substrates lb-g. These were synthesised in a of bisnaphthols adopting the two step process involving preparation _ with oxidation subsequent and their procedure’ Shearing and Smiles substrates lb-g, When the NH2OH reaction was carried out with K$?e(CN)S. the

these

corresponding pyrrolotropones 2b-g, were formed. All

R,

= RL

= R5

= R6

= H

RI = R,,

= R5

z R6

= t-j

b,

R2 = R3=Br

C)

R2 =Rj=OMe;

d)

R2 = R3 = DC”3

e)

R2=

f)

Rl=R/+=CH3j

9)

Rg=Rs

h)

R5=CH3

; R,=R2=R3=R11=R6zH

t)

R6 =CH-J

j

h

R2=R6z~-B~i

kl

R\=CHjj

R,

RI =Br

=R2tiR3= =

R+J=R~

= t-t =H =H

R4 =R5 R3=Rh

=

t-t

d$=H

zR~=R~

= H

= R2 = R-J = Rh = Rg = H i

R1=R3=R j

=

RI=R~=R~zR,+

Rz= j

zR6

R2=R3=R5=R6

R,

R2=R~=~5

R3=Br

R, = R4 =R5 Rl=R4=R5=R6

=CH3j

rl) R-J=B~; 0)

;

R3 = i-bu;

1) R5 = Br m)

;

RI

= R4 =R~ 4=R5=Rg

RI =R2=R4=R5=R6=ti Scheme 2

= H = H

H

compounds

Compd.

-

6.93 (d,z=12.0)

(4.$!3.1)

3250-3150 1615 20

9.04tNH)

9.12(d.J=8.4,&H,ArH)

,d,&:Z.S,

3250-3150 1620

6.94 (d,J=lZ.S)

3250-3150 1630 2m 2n

6.99 (d,J=12.5

,d,$9,3.1

-

3250-3150 1630

3300-3200 1620

3300-3200 1620

21

226(24,C56) 282(18,239) 299(19,081) 308117,984) LiSS(9.974)

-

7.08 (d,J=12.7,

of

the signals

13.05tNH)

7.5-9.4(m,lZH,ArH)

7.65-9.62(m.9H.ArH) 13.20(NH)

7.47-9.19(m,lOH,ArH) lZ.SO(NH)

7.52-9.48(m,lOH,ArH) 12.25(NH)

2.79(S,ArCH,) 7.49-9.04(m;12H,k-H) 12.9(NH)

12.68(~~)

1.4(s,9H.t-Bu.1 1.53Ls,SH:t-bu) 7.45-8.84(&11H,A:H)

2.6 (d,J=O.S.C13-CH ) 7.46-9.~0(m,11A,k-H~ 9.26(NR)

*

2.75(s,ArCH,) 7.4-8.12~m,IOIi,ArRl 9.181NH) 9.38(d,"8.6,1H,ArH,

Rest

__,;;______ir_r:?_!rs__________

2.59*(d.J=0.8.C13-CA31 2.70(s,ArCH ) 7.43-8.02(m!9H,ArH)

2.73(s,ArCH3) 2.89(s.ArCH ) 7.66-9.4(m,%i,ArH) 12.86(NH)

3250-3150 1620

21

220[16,752) 3200-3100 246(16,'069') 1615 ZSl(15.889) 308(11,533) 363(5605)

220(14,126) 248(13,446) 283(15,6103 309~12.225) 362(5,456)

x

1H NMR of 2e and 29-i were recorded in CDCl w spectra were recorded in EtOH; and the others in DMSO-d ; chemical shifts are in CT values; J values are in Hz;' NH signals are D20 exchangeable; 'Signal of mezhyl Oc to the ketone in fgranotropones appears aroundd 2.6 (see ref.18)

3300-3200 1625

2g

‘1

2k

7.c9

1.44(s.&-Bu),, (d,;=12.4) 1.45(s,t-Bu) 7.28-S.b6(m.SH.ArH) 9.301NH) 9.38(d.J=9_0,1H,ArH)

3300-3200 1620

3300-3300 1620

366(5476)

282114,965 309(9047)

250(9,523)

224( .2,006‘1

Zf

2e

2j

6.92 1.26(s,6H;Ze+ (2,3=12.7) 1.4-1.7(m.l6H) 2.14(m,4H) 7.6-9.41(m,9H,ArH) 12.84(NH)

21

3300-3150 1620

2d

3.95(s.0CH3) 7.21-9.46(m,9H,ArH) 12.751NH)

3.90(S,0CH3)

6.92 td,p=l2.8,

2h

NO.

Compd.

3250-3150 1620 1505

2c

7.5%9.40(m,9H,ArH)

Rest of the signals

____________-------

1H N?lRdata

and 1H NNR spectral data of pyrrolotrcpones Zb-o

13.15(NH)

6.9

_______-w-m--Cl5

W,IR

(d,;=12.4)

3250-3150 1620

A

2b

NO.

Table I.

E a ?

E

:

.s

117

Reactionofspironaphthalenoneswithhydroxyhunine-I

doublet signal

exhibited the characteristic

8

for the < -proton of the enone

system in the tropone ring around 6 6.9 in addition to the aromatic

and the

NH protons [vide Table I]. to

order

In

find

spironaphthalenone

out

which

responsible

is

rings

the

of

for the formation

(A

or

B)

the

of

in

tropone,

the we

synthesised unsymmetrical

substrates lh-m for reaction with NH2OH. Reaction 3) with 2-hydroxy-1-naphthylmethane (9a, Scheme of 3-methyl-2-naphthol lOa-c sulphonate (8) in N/3 NaOH solution gave a mixture of bisnaphthols formation which could be separated by rigorous column chromatography. The catalysed desulphomethylation of 8 to sulphomethyl anion (OHCH2SO; )I which has been sulphomethylation postulated as the actual reactant in previously 9 rise to 2sulphomethyl anion to 9a would give of reaction . Addition of

these

bisnaphthols

can be explained by

hydroxy-3-methyl-l-naphthylmethane and

the

sulphonate

methane

Table II. Compound No.

1 H NMR

base

sulphonate(l2a).

Condensation between 9a of 3,3'12a would result in the formation

spectral data

for

spironaphthalenones

1

H NMR data ---------------------------------_____________________________,_ oC-enone

19

lh

initial

the

-

Rest

of

the

signals

3.5O(d,J=15.6,lH,Ha) 3.97(d,~=15.6,lH,Hb)

2.07(d,J=1.2,3H,C3-CH3) 2.53(s,TH,C4'-CH ) 7.24-7.77(m,lOH,&H)

3.5l(d,J=15.6,1H,Ha) 3.99(d,z=15.6,1H,Hb)

2.07(d,J=1.2,3H,C3-CH3) 7.24-7.85(m,llH,ArH)

li

6.25 td,J=lO.l)

3.51(d,J=15.6,1HIHa) 4.04(d,z=15.6,1H,Hb)

2.53(s,3H,C4'-CH ) 7.2577.77(m,lOH,;lrH)

lj

6.22 (d,J=10.2)

3.60(drJ=15.6,1H,Ha) 4.15(d,J=15.4rlH,Hb)

1.38(s,9H,t-bu) 1.56(s,9H,F-Bu) 7.3-7.9(m,FH,ArH)

lk

6.24 td,z=lO.2)

3.52(drJ=16.7,1H,Ha) 4.08(d,z=16.7,1H,Hh)

2.70(s,3H,C6-CH 7.2-7.97(m,lOH,&H)

lm

3.53(d,J=16.0,1H,H 4.03(d,~=l6.O,lH,H;:)

)

7.44-7.99(m,9H,ArH)

3.47(d,J=15.4,1H,H 4.05(d,J=15.4,1H,H;:)

)

7.2-7.95(m,lOH,ArH

(d,;::O.l)

3.50(d,J=15.6,1H,H 4.06(d,J=15.6,1H,H;:)

)

7.2-7.9(m,lOH,ArH)

(d,$;O.2)

In lo

'H NMR spectra of lj, In and lo were recorded others at 270 MHz (CDC13), chemical shifts are are in Hz.

at in

)

1

90 MHz (CDCl ) and d values; J3values

t

R2=H

Br

Rl = R5 =CH3;

C)

R2=R3=RL=

R2 = R3 = Br j RI= Rb =R5 = H

b)

=R4 = R5 = H

Rl = R2 =R3

a)

H

N/3 NaOH

d) R1 = R3 = H j R2=CH3

C) Rl=R3=t_Buj

q

; R2=R3=H

OH

b) R1 = R2 = H j R3

a) RI tCH3

= >

j,

i)

h)

Rj=Br

R3=R5

= t_Buj

3

Rl=R2=Rb

Rl=R2=R3=Rb=H

Scheme

R5=CH3j

RI =CH3 j R2=R3=RL=R5=

RL4

R1= R2= H j

b)

R2 =R3=H

RI:

a)

CH3j

9,aP

T

-I8

OH

00

OH

R5

=H

H

e)

d)

R3=

Br

O) RZ=Br

n) R3= Br;

j Rj=Rs=Rh=R5

RI =R2=RL=R5

Rl=R2=R3=R5

>

=H

= H

= H

R5 = H j R3 = R~ = Br

R5=Hj

k) Rb = CH3j

Rl=R2=

R1 rR2=R4z

RI = R5 = CH3 j R2 = R3 = R,s, = H

RI = R2 = R3 = RL = R5 = H

b) C)

RI = R2 = R3 =RA =Hj

R5=CH3

K3 [FeW6]

a)

R2

Rl

OH

m

R3

%

2: 5 Q a .-

!+ P

119

Reaction ofspironaphthalenoneswith hydroxylamine-I

disubstituted naphthol

bisnaphthol lOc, while that between 8 and the generated

would

give

rise to lob. Bisnaphthol 10a would

arise

p -

from

the

expected coupling between 8 and 9a. Similarly, when the condensation of

6-

bromo-2-naphthol (9b) with 2-hydroxy-1-naphthylmethane sulphonate(8) was carried out and the resulting bisnaphthols oxidized with K3Fe(CN16, spironaphthalenones

la,b,n

&

o

were

isolated

after

purification

by

preparative TLC. The formation of spironaphthalenones la,b,n & o indicated that the condensation of 8 with 9b has resulted in the formation of bisnaphthols lOb,d & e. This is in conformity with the above mentioned findings and is contrary to the results obtained by Shearing and SmileslO who report the isolation of only one bisnaphthol. Spironaphthalenones Ih i

were

obtained

followed

by

evident cC-enone

by the oxidation of the mixture

purification

of

bisnaphthols

by preparative TLC. Structures

of

(L

lOa-c

these

were

from 'H NMR . While compound li gave a doublet at d 6.25 for the proton, it was absent in lh. Oxidation product of a mixture of

bisnaphthols prepared by coupling of 3,6-di-&-butyl-2-naphthol

(9c) with

8

separated by rigorous column chromatography to yield lj which was characterised by the 1H NMR doublet at 66.2. Following similar procedure, spironaphthalenone lk was prepared by the reaction of 9d with 8. Spironaphthalenone Table II lm (see for data of spectral spironaphthalenones) was prepared by bromination of dibromoketone Ib

was

followed by dehydrobromination of the resulting bromo adduct, adopting the procedure of Shearing and Smiles 10 . 3 reaction of According to the mechanism proposed by Dean -et al., spironaphthalenone pyrrolotropone product l1

(

2i.

lh

M+, 309)

corresponding

to

with

When

NH20H

should

result

the reaction of lh was

exhibiting

the Oc -enone

a doublet proton

was

at

in

the

carried 6 7.08

formation out,

(2

obtained.

=

a

of

single

12.7

Further,

Hz) the

characteristic UV absorption pattern of pyrrolotropone was observed

(Table I). Based on the spectral data, structure 2h was assigned to this product. The isomeric pyrrolotropone 2i expected from Dean's mechanism should not show a doublet around 6 6.9 . When the reaction was carried out with the spironaphthalenone li carrying a methyl group in the naphthalene ring, the resulting pyrrolotropone exhibited no doublet corresponding to the Kproton

of

the enone system, implying that the methyl group is in the tropone ring QC to the keto group as in 2i. Reaction of lj with NH20H gave the pyrrolotropone 2j (no doublet at d 7.0 region;r-butyl group is cCto the keto).

Pyrrolotropone 2k results from the reaction

lk. gave

of

spironaphthalenone

Spironaphthalenones 11 & m carrying bromo substituents at C3 rearranged pyrrolotropones 21 & m showing the characteristic

aroundd7.0

position doublet

region for the <-enone proton (Table I). It is obvious from the

120

T.R.KASTUIU~~U~.

above

experiments that it is the ring A,but not the ring B spironaphthalenones that is transformed to the tropone ring pyrrolotropones.

of

the

of

the

The present work has clearly demonstrated that: (i) furanotropone 6 is not an intermediate in the formation of pyrrolotropones;(ii) only one of NHZOH

is

mole required in the reaction and(iii) ring A and not the ring B of

spironaphthalenone

is

converted to the tropone ring.

In view of these findings, which are not in accordance with Dean's mechanism 3 , an alternate mechanism has to be visualised and further work is in progress in this direction. Experimental Section All m.ps reported herein are uncogfected. UV(nm) spectra were recorded on a Shimadzu spectrophotometer. IR(cm ) spectra were recorded either on a Hitachi Model 270-150 double wavelength/double beam or Perkin-Elmer Model 781 instruments. H NMR data was recorded on a JEOL FX 90 Q (90 MHz) or a Bruker-WH-270 (270 MHz) instrument using TMS as an internal standard. Mass spectra were recorded on a JEOL MS-DX 303 spectrometer operating at 70 eV and fitted with a built-in inlet system. SpironaphtP$egones procedures .

lb-e

:

These were

prepared

according

to

reported

: Sodium salt of 2-naphthol-l3-Methyl-bis(Z-hydroxyia-naphthyljmethane methane sulphonic acid (8 ,1.2 gm) and 3+methylL2-naphthol (800 mg) were dissolved in N/3 NaOH solution (30 ml) and refluxed for 6 hrs.The solution was cooled and neutralised with dil.HOAc. The white solid which separated out was filtered, washed with water and dried (850 mg). The mixture of bisnaphthols, thus obtained, was separated by column chromatography (silica gel, benzene-CHC13) toogive (i) bis(3-methyl-2-hydroxy-1-naphthyl)methane IR (nujol) 3300-3350, and (lOc, 429 mg);lm.p.208 C (d) (CHCl -hexane) ; 1610 cm ; H NMR (270 MHz; DMS&d6) 2.39 ( s,6H,2+ArCH ), 4.83 ( s, ZH,benzylic CH2), 7.30-8.18(m,12H,ArH) ;MS; m/e 328 (M , 681 309 (17), 171 (62) and 158 (lOO%).Anal.Calcd.for C (ii) 3_methyl_bis3&0C2: c8 84*12; H, 6.14**ol;ndlo;; 83.96; H, 5.90%. ydroxy-l-napthyl)methane 390 mg); m.p.179-180°C(CHC13-hexane) ; IR (nujol) 3300-3400, and 1630 cm- ; H NMR (270 MHz, DMSO-d6) 2.37 ( s,3H,ArCHl, 1, 4.82 ( s,ZH,benzylic CH2 ), 7.07-8.24 ( m, 13H, ArH); MS; m/e 314 (M , 24) 171(13), 158(73) and 144 (100%). Anal.Calcd.for 84.05; H, 5.77.Found 5.49%.7ando(iii) bis(2-h~&?~02in~phthyl)methane(10b, 30 Agyi m8i:2gi99ak (lit. 199 C). : To a mixture of bisnaphthols Oxidation of bisnaphthols 10 with K Fe(CN) lOa-c obtained in the above coup1 ?ng rea b tion(8 gm) in 10% KOH solution (300 ml) was added K Fe(CN) (17 gm) and the mixture was stirred for 3 hrs. Extraction with CH2 2 l2 followed by removal of solvent left a yellow solid (5 gm) which was separated by careful column chromatography (silica gel, CHCl -hexane mixtures) to give four compounds identified as : (i) 3,4'dime shyl-spiro(naphtha&ene -1(2~),2'(1'fi)-naphtho[2,1_blfuran)-2-one -1 ; MS; (lg,2.2 gm); m.p.;153 C (CHCl -hexane);IR (nujof) 1660 and 1630 cm m/e 326 (M+, 88), and 310 (laO%);Anal.Calcd.for C23H 802: 5.52. Found C, 84.7; H, 5.5%. (ii) 3-methyl-spiro~naphth~~en~~~~!~2fi~~ 2'(1'H)-naptho[2,1-b]furan]-2=yne (lh,1.2 gm); ~.p. 133OC (acetone-texT;;i; IR (nujol) 1670 and 1620 cm ; MS; m/e 312 (M , 7) 295(100), I 139(15) and 120(18%).Anal.Calcd.for C22H1602: C, 84.68; H, 5.25%. Found C,

Reactionofspironaphthalenones withhydroxylamine-I

121

84.61; H, 5.22%. (ii+) 4Lmethyl-spiro~~aphthalene-l~2~),2'(l'H)-napththo [2,1-b]furan)=j-one (11,1.3 gm); T.p.139 C (CIiCl-hexane); IR(Gjo1) 1670 and 1600 cm ; MS; m/e 312 (M , and 239(33%); Anal. 70), 295(laO) Calcd.for C22H 0 : C, (iv) Sp~rolnap~~Q~lene_l~2;;;43; F, 5.12. Found C, 84.65; H, 5.15%. 2 (1 g)-naphtho[2,1-b]furan)2-one(la,100 mg), m.p.171 C (lit. , 171-172 c). 6,7'-Dibromo-spiroInaphthalene-l~2~),2'~1'H_)-naphtho[2,1-b]furan)-2-one(lb) and spironaphthalenones In & o: Sodium salt of 2-naphthol-l-methane sulphonic acid (2.6 gm) and 6bromonaphthol (3.5 gm) were dissolved in N/3 NaOH solution (97 ml) and refluxed for 6 hrs. The solution was cooled and neutralised with dil.AcOH. The white solid which separated out was filtered , washed with water and dried (2.5 gm). To the above mixture of bisnaphthols (1 gm) in 10% KOH solution (30 ml) was added K Fe(CN) (1.6 gm) and the mixture was stirred for 3 hrs. Extraction l2 followed by removal of solvent left a yellow solid w a th CH2 fi (600 mg) which was separated by PTLC (Silica gel, benzene:hexane )into four compounds which were identified as:(i) 6,7'-Dibromo-spiro(gaphthaleTT1(2H),2'(1'~)-naphtho[2,l+b]furan)_2-one (lb,120 mg); m.p.197 C (lit. 196°C) . (ii)6-Bromo-spir@naphthalene- 1(2g),2'(11g)-nqhtho[2,1-b]furpn)-21 one{10 ,110 mg); y.p.182 C;IR(nujol):1665 and 1630 cm ; MS;m/e 377(M ,70%) :ii) 7'-Bromo-spiro(~aphthalene-l(2~),2'(1'H)~o[2,l-b]furan)-~-one n, 100 mg); m.p.185 C;IR(nujol) 1670 and 1620 cm ; MS;m/e 377(M ,67%). (iv) Sp@otnapQ$halene-1&2H),2'(l'g)-naphtho[2,1b]furan)-2-one (la,120 mg) m.p.171 C (lit ,171-172 C ). 6'-Methyl-spiro(naphthalene-l~Z~),2'~l'~)-naphtho[2,l-b]f~~an)-2-one (lk): A mixture of sulphonate 8 (7.72 gm), 5-methyl-2-naphthol (5 gm) and N/3 NaOH (190 ml) was refluxed for 6 hrs. The reaction mixture was cooled, neutralised with dil.AcOH and the resulting solid was filtered, washed with water and dried (5 gm). A solution of this solid (5 gm) in 10% KOH (187 ml) containing K Fe(CN) (10.62 gm) was stirred for 3 hrs. The reaction mixture was 2 xtractgd with CH Cl washed with 5% NaOH, water and dried. The residue obtained after ZemGal of solvent was purified by column chromatography (silica gel, benzene) followed by repeated fractional 1670 crystallisatipn to give lk (140 mg); m.p. 173-174OC (CHCl -hexane);IR and 1630 cm . Anal.Calcd.for C22H1602: C, 84.63; H,5.122. Found c,84.49; H, 5.13%. 2'(1'fi) naphtho[2,1-b]furan)-2-one 3,6,7'-Tribromo-spiro(naphthalene-1(2!), (lm): A solution of spironaphthalenone lb (500 mg) in glacial HOAc (5 ml) containing bromine (280 mg) was stirred for 2 hrs.at O°C followed by 6 dilution with hrs. at room temperature (25OC). The solid obtained after water (50 ml) was filtered and dried to give 3,4,6',7'-tetrabromo-spiro mg); (3,4-dihydro-naphthalsne- 1 (2 H),2'(1'H)naphtho[~ll-b]furan)-2-one(800 m.p (crude) 140-142 C (d); IR(nujolT 1730 cm H NMR (90 MHz,CDCl ) lH,benzylic 3.53(d, J= 16.0 Hz, lH,benzylic CH), 4.26(d,J=16:0 Hz CHj, 7.22-8.0(m,8H, 4.96(d, ;i= 3.0 Hz, lH, C3-H), 5.42(d,J=3.0 Hz,lH, C4&) ArH) an analytically pure sample could ?iot, however, be ob;ained. A solution of the above crude bromo compound (800 mg) in pyridine (10 ml) was stirred at 60°c for 8 hrs., neutralized with dilute HCl (50 ml) and with extracted with CHC13 (3x25 ml). The chloroform extract was washed water and dried. The product obtained after removal of CHC13 was purified ( neutral alumina) CHCl as using eluent. by column chromatography 198-3199 C Crystallisation gave yellow needles_pf lm(420 mg); m.p (CHC13hexane) ; IR (nujol) 1695 and 1635cm ; MS; m/e 532(M ,lO%).Anal.Calcd.for C21H11Br302: C, 47.16; H, 2.05. Found: C, 47.14; H, 2.08%.

122

T.R.KASTURI et al.

:;j:'-Di-&-butylspiro(naphthalene-1(2fi), 2'(1*H)-naphtho[2,l-b]fufan);E;;!t : To a mixture of sodium salt of 2-naghthol-l-methanesulphonic 8 (3.24 gm) and 3,6-di-t-butyl-2-naphthol (9c ,3.4 gm), N/3 NaOH (80 ml) was added and refluxed For 6 hrs. The solution was cooled, neutralised with dil.AcOH and the resulting white solid was filtered, washed with water and dried (3.54 gms). A mixture of this solid (3.54 g) and K Fe(CN) (4.68g) in 10% KOH (98 ml) was stirred for 3 hrs. The reaction mix sure wa 8 extracted with CH Cl , washed with 5% NaOH, water and dried. The residue obtained on removal' 03 sol vent gave on column chromatography &silica gel, benzenehexane) the title compound1lj (150 mg); m.p.168-169 C (CHC13-hexane); IR (nujol) 1665 and 1625 cm . Anal.Calcd.for C2gH3002: C, 84.81; H, 7.35 Found C, 85.19; H, 7.13%. General procedure for the reaction of spironaphthalenones lb-o with NFI OIi.HC.1: NH OH.HCl (3 mmol) in ethanol (4.5 ml) was added to the sp&onaphthalenke (1 mmol) in THF (1.5 ml). A drop of conc.HCl was added and the mixture heated under reflux for 24 hrs. The solid that separated was washed with ethanol and recrystallised from DMF. All the compounds melted above 360°C. 3-lO-Dibromo-14H-benzo[6,7]cyclohepta[l,2-b]naphtho[l,2-d]-indole-l4-one (2b): Reaction- of lb with NH OH.HCl gave 2b(250 mg) . Anal. Calcd. for C21H11Br2N0 : C, 54.86; H, 2.63; N, 2.82. Found C, 54.84; H, 2.85; N, 2.98%, 3,10-Dimethoxy-14~-benzo[6,7Jcyclohepta[l,2-b]naphtho[l,2-d]indole-l4-one (2c):Reaction of lc gave 2c(250 mg).Anal.Calcd.for C23H17N05: c,77.75; H, 4.79; N, 3.94.Found C, 77.79;H, 4.86;N, 3.80%. 3,10-Di-(l-methylcyclohexyl)-l4H-benzo[6,7]cyclohepta[l,2-b]naphtho[l,2-d] inqole-14-one :Reactioz of Id gave 2d(255 mg);MS; (2d) m/e C35H37NO: C,86.24; Anal. Calcd.for H,7.60;N,2.87.Found (M , 39%). 85.83; H, 7.73; N, 2.74%.

487

C,

3,10-Di-~-butyl-14~-benzo[6,7]cyclohepta[l,2-b]naphtho[l,2-d]indole-l4-one (2e): The reaction of le with NH20H.HC1 gave 2e/250 mg) .Anal.calcd.for C2gH2gNO: C, 85.51;H, 7.16;N, 3.42.Found C, 85.41; H,7.12; N, 3.48%. 4,11-Dimethyl-14H-benzo[6,7]cyclohepta[l,2-bJnaphtho[l,2-dJindole-l4-one (2f) : Reaction zf If gave 2f(200 mg).Anal. Calcd.for C23H17NO: C, 85.42;H, 5.21;N, 4.38. Found C, 85.36; H, 5.25; N, 4.29%. 6,13-Dimethyl-14~-benzo[6,7]cyclohepta[l,2-b]naphtho[l,2-d]indole-l4-one (2g): The reaction+of spironaphthalenone lg with NH20H.HC1 gave 2g(l55 mg); 323 (M ,62), 295(100), 278(28) and 162 MS ; m/e (57%). Anal.Calcd.for c, 85.43; H, 5.32; N, 5.04.Found C, 85.67; H, 5.68; N, 5.22%. C23H17NO: 6-Methyl-14H-benzo[6,7]cyclohepta[l,2-b]naphtho~l,2-d]indole-14-one (2h): 07 lh gave 2h(195 mg) ;MS; m/e 309 (M ,331, 295(8) 281(100), and Reaction 266(8%). Anal.Calcd.forC22 H 15NO C, 85.41;H, 4.89; N, 4.53. Found C, 85.07; H, 4.69; N, 4.41%. 13-Methyl-l4~-benzo[6,7]cyclohepta[l,2-b]naphth~[l,2-d]indole-l4-~~~ Reaction of li gave 2i(160 mg); MS; m/e 309 (M , 621, 2814(iz), H, . : and 139 (100%). Anal.Calcd.for C22H15NO: C, 85.42: Found C, 85.08; H, 5.22; N, 4.91%.

N,

10,13-Di-~-butyl-14H-benzo[6,7lcyclohepta(l,2-blnapth~~l,2-blindole-l4-one (2j): Reaction of 17 gave 2j(250 mg) ; MS; m/e 407 (M , 100), 392 (36) 379 (25%). Anal.Calcd.for C2gH2gNO: C, 85.52; H, 7.11; N, 3.45. Found 85.38; H, 7.12; N, 3.46%.

(2i): (651, 4.53.

and C,

123

Reaction ofspironaphthalenones withhydroxylamine-I

ll-~thyl-l4~-benzo[6,7lcyclohepta[l,2-blnaphthoClr2-dlindole-14-one (2k): Reaction of lk gave 2k(220 my). Anal.Calcd.for C22H15NO: C, 85.71; HI 4.82; N, 4.53. Found C, 85.60; H, 4.95; N, 4.11%. 6-Bromo-14~-benzo[6,7]cyclohepta[l,2-b]naphtho[l,2-d)indole-l4~ne (21): Reaction of 11 gave 21(160 mg); MS; m/e 375, 373 (M , l:l, 731, 345 (100) and 264 (55%). Anal.Calcd.for C 21H12BrNO: C, 67.36; H, 3.21; N, 3.70. Found C, 67.57; H, 3.02; N, 3.62%. 3,6,10-Tribromo-14~-benzo[6,7]cyclohepta[l,2-b]naphtho[l~2-d]indole-l4-one (2m): The reaction of spironaphthalenone lm with NH OH.HCl gave 2m(180 mg); MS; m/e 529(M , 25%).Anal.Calcd.for C21H10Br3NO: 6, 47.3; II, 1.8; N, 2.64 Found C, 47.2; H, 1.8; N, 2.62%. l0-Bromo-14H-benzo[6,7]cyclohepta[l,2-b]naphtho[l,2-d]indole-l4-one (2n): Reaction or In gave 2n(160 mg). Anal.Calcd.for C21H12BrNO: C, 67.37; H, 3.21; N, 3.70. Found C, 67.21; H, 3.19; N, 3.70%. 3-Bromo-l4-~-benzo[6,7]cyclohepta[l,2-b]naphtho[l,2-d]indole-l4-one (20) : Reaction of spironaphthalenone lo with NH OH.HCl 20(160 mg). Anal.Calcd.for C21H12BrNO: C, 67.37; H, 3.21; 2, 3.70. F:::: C, 67.32; H, 3.15; N, 3.67%.

ACKNOWLEDGMENTS thank Sophisticated Instruments Facility, Bangalore for the NMR We spectra and Chandrika Kasturi (OSU, Columbus, USA) for a few of the mass spectra reported herein. We also 'thank Prof. K. Venkatesan and his coworkers for the X-ray crystal structure analysis. Financial assistance from Council of Scientific and Industrial Research and Indian National Science Academy, New Delhi, is gratefully acknowledged.

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Chem. SOC., 1963, 393; Dean, F.M.; Locksley, H.D. J. -Chatterjea, J.N. J. Ind. Chem. sot., 1950, 27, 375; 1958, 35, 37; Sestan],K.Arkiv. Kern., 19r23, 81.

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5.

Reddy, G.M. 1985.

6.

For convenience ,we have also used 3 moles of NH OH in subsequent reactions. We have also shown that the oximes pr Z pared from a few are converted to the products without the use spironaphthalenones of NH20H (Part III of this series).

7.

Shearing, E.A.; Smiles, S. --J. Chem. SOC., 1937, 1348.

'Ph.D Thesis', Indian Institute of

Science,

Bangalore,

T. R. KASTURI et al.

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11.

TLC (EtOAc /CHCl varying proportions)showed the presence of only one compound. HP& also indicated the presence of only one compound using (retention time 6 min onla Water's Microbondapack Cl8 column methanol as the eluent). H NMR spectra of the crude and the purified product were identical.

12.

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