Oct. 5 , 1933
GRIGNARD REAGENTS ON
[CONTRIBUTION FROM
THE
NAPHTHO-(2’,:3’)
312i
-0XAZOL-%ONES
CHEMISTRY DEPARTMENT, FACULTY O F SCIENCE, CAIRO UNIVERSITY]
Action of Grignard Reagents. VIII. Action of Organomagnesium and Lithium Compounds on Benzo-, Naphtho-(2’,3’)-oxazol-2-ones and their N-Substituted Derivatives BY AHMEDMUSTAFA, WAFIAASKERAND ORKEDEHASSANHISHMAT RECEIVED APRIL19, 1955 Treatment with Grignard reagents, followed by hydrolysis, caused the opening of the hetero ring in benzo- and in naphtho(2’,3’)-oxazo1-2-onesand their N-aroyl- and S-arylsulfonyl derivatives to give the corresponding Xi-aroyl-and S-arylsulfonyl derivatives of o-aminophenol and of 3-amino-2-naphthol. Similar results were obtained with phenyllithium. Similarly, the action of phenylmagnesium bromide yields 3-keto-1-phenyl-1-hydroxyisoindoline and triphenylcarbinol in the case of Sbenzoylphthalimide, benzotriazole and triphenylcarbinol in the case of 1-benzoylbenzotriazoleand a,a,&&tetraphenylbutylene glycol and p-toluenesulfonamide in the case of N-p-toluenesulfonylsuccinimide. Phenylmagnesium bromide also brought out the cleavage of N-C bond in N-benzenesulfonylbenzanilide to give benzenesulfonanilide and triphenylcarbinol,
Recently i t was shown t h a t phenylmagnesium bromide cleaves the oxazolone ring1 in 4-methyl-2phenyl-5oxazolone ( I ) , forming 2-benzoylamino1,l-diphenylcarbinol (11). HyCCH--S
C6H,MgBr,
~
o=C CGH, \O/ I
hydrolysis
HIC-CH-XH
I
1
( CfiHs)2COHCOC6H,
I1
We now have investigated the action of Grignard reagents on benzoxazol-%one (IIIa), naphtho-(2’,3’)-oxazol-2-one (IVa),* their aroyl- (IIIc) and ( I n ) , arylsulfonyl derivatives (IIId, IIIe and IVc) and 3-acetylbenzoxazol-2-one(IIIb), respectively. R
R
mal or the inverse addition,3 give Va and VIa, respectively, together with triphenylcarbinol. Similarly, N-(p-toluoy1)- (Vb) and N-(1-naphthoy1)-oaminophenol (Vc) are obtained by the action of ptolyl-, and of 1-naphthylmagnesium halides together with di-(p-tolyl)-phenylcarbinol and di-( 1naphthyl)-phenylcarbinol, respectively, on IIIc. The action of 1-naphthylmagnesium bromide on I V b gives rise to N-( l-naphthoyl)-3-amino-2naphthol (VIb) and di-( 1-naphthyl) -phenylmethylcarbinol. Va similarly is obtained together with diphenylmethylcarbinol by the action of phenylmagnesium bromide on 3-acetylbenzoxazol-2-one (IIIb) . It is believed that the formation of the N-aroyl derivatives Va-c and VIa-b proceeds via the sequence of reactions indicated in the scheme MgX
I
I’
A
When I I I a is treated with an excess of phenylmagnesium bromide and the product hydrolyzed, N-benzoyl-o-aminophenol (Va) is obtained. Similarly, N-benzoyl-3-amino-2-naphthol(VIa) has been prepared by the action of the same reagent on IVa.
hpdrol.
VIa, R
=
hydrolysis +- Q-OH
COCfiHs; b, R = COCloH7-1; c, R = S02CaHs
3-Benzoylbenzo- (IIIc) and 3-benzoylnaphtho(2’,3’)-oxazo1-2-one (Ivb), on treatment with excess of phenylmagnesium bromide both b y the nor(1) Cf. “The Chemistry of Penicillin,” H. T . Clarke, J. H. Johnson and R. Robinson, eds., Princeton University Press, Princeton, N. J . , 1949, p. 738. (2) Cf. the formation of 3-phenyl-2-benzylbenzothiazoleniumperchlorate by t h e action of benzylmagnesium chloride on 3-phenylbenzothiazol-2-one, followed by t h e addition of perchloric acid (H. Passing, J. p r a k t . C h e m . , 163, 5 (1939).
R‘MgX hydrol
R*‘(CsKs)COH H I
CsHSMgBr, / , --“R IIIa
I
r____.+ $
O$gH
-0
/ -”COR’ \ -OH
Likewise, treatment of I I I c with phenyllithium gave results which are similar to those obtained with phenylmagnesium bromide. Whereas arylmagnesium halides effect the elimination of the benzoyl group in IIIc and I v b , methylmagnesium iodide reacts with IIIc, producing fission of the hetero ring with the formation of Va and t-butyl alcohol. 3-Benzenesdfonyl- (IIId), 3-p-toluenesulfonylbenzoxazol-2-one (IIIe) and 3-benzenesulfonylnaphtho-(2’,3’) -0xazo1-2-one (IVc) undergo hetero ring fission by the action of phenylmagnesium bromide, yielding N-benzenesulfonyl- (Vd) , N-p-tolu(3) Cf.t h e normal and inverse addition of Grignard reagents t o 2methyl-3,1.4-benzoxaz-4-one(W. C. Lothrop and P. A. Goodwin, THISJOURNAL, 66, 363 (1943)).
enes~zlt^onyl-o-~niinophen~l (Ye) and N-benzenesulf ,Iiyl-3-amino-'-naphthol ( T I C ) , respectively, toirether with triphenylcarbinol Similarly, Vd and tri-1-naphthylmethylcarbinol are obtained by the 'iction of 1-naphthylmagnesium brornirlc. 0 1 1 IIItl icf scheme -\) The stability of the S-arylsulforivl l i n h ~ g eto ward the Grignard reagent 15 contrasted with the ready elitnination of the aroyl groul) .itt,tclietl to i h i nitroZen atom by this reagent ?JgBr
!I
R'lIgBr IC1
-+
/
,/
1
-
\SO C,FI o\IgBl
1
- R' c
(X) are obtained.6 The behavior of IX towartl Grignard reagents may be compared with its btahavior toward lithium aluminum hydride.' S-!,-.Toluenesulfonylsuccinimide (XI1i, which is closely related to VHb, reacts analogously with (;rignard reagents. 'Thus XI1 undergoes ring ope11 ing la>- the actioii of phenylmagIiesiurri brorriiclc., yielding a,a.,6,6-tctraljhc!iylbutyleiie glycol (XI 1 I together with /~-tolueiiesulfon3rriidc.. XI11 is (lehydrated readily by the action of glacial acetic aciti and hydrochloric acid to a ,a,6,6-tetraphenylbut:ldiene. 1
0
,
0
c F f -?c - ~ s s o ~ c , , f f ,. -cCiiHsMgRr ------+ !~~.p 13
cir: c,
liytlrol.
I
0
SI1
R'GC .Or I
I I,C-~-C(CbH:),OIt
Scheme A
2- p-crI L , , lT,SO?SI I: The action of phenyllithium on I I I d led to results H:C-C( CsH;)?OH which are similar to those obtained with phenylSI11 magnesium bromide. Recently blustafa and co-workersY have shown For a further study of the effect of the aroyl- and that phenylmagnesium bromide effects the cleavage of the arylsulfonyl group attached to a heterocyclic of the N-S and "2 linkages in N-dibenzenesulnitrogen compound on the hetero ring opening with fonyl- and ?:-dibenzoyl derivatives of aniline, Grignerd reagents, the action of phenylmagnesium yielding benzenesulfonarnide together with tlibrornitle on N-benzoylphthalimide (TTIIai and on phenylsulfone and benzanilide together with tri1 -berizo.ilbenzotriazole JIXi now has been investi- phenylcarbinol, respectively. \Ye now have found gated. Thus, whereas X-bemenesulfonplphthali- that when the mixed aroyl arylsulfonyl derivative, niitle j7
