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Organotellurinic acid anhydrides as selective oxidants in organic synthesis
Tetr~ Fvinwd
Vol. 41 No. 8, pp. 2319 to 2324.1986 in chal miti.
ORGANOTELLURINIC
ACID
Derek
ANHYDRIDES
H.R.
lnstltut
Barton,
AS SELECTIVE
Jean-Pierre
OXIDANTS
IN ORGANIC
Flnet and Martial
de Chlmle des Substances
Naturelles,
91190 Clf-sur-Yvette,
SYNTHESIS
Thomas
C.N.R.S.,
France
(Recekd in Frmux 6 Jammy 1966)
acid anhydrides have been compared lbr their Abstrvct - Sever01 aryltellurinlc oxldising properties in acetic acid. Very high yields of quinones and disulphides can be obtained under candltlons where phenols are not oxldlsed.
Dlanisyltelluroxide thiols
to disulphldes
phenols
or
formation often
and
amlnes.
Many
thlones
of a diaryltelluride.
oxidised,
provided
propertles
for example,
have
hydrazlne
mild and selective The ponding
aromatic
through
i.
aryltellurinlc
anhydride
agents
aryltellurinic
of the latter
and The
soluble
soluble
in acetic
on heating
reactivity
Table
acid (and
Synthesis
like
therefore,
ketones
that
other
for
aryltellurlnlc
oxldlse
presence
sulphur
of
wlth
functions
are
is present. some time. 283
reduction
Their
to ditellurides
by,
acid anhydrides
are
diaryltelluroxides. prepared
tetrachloride
lose water
to give
solvents.
aclds).
in acetic
Anhydrides
the corres-
the trlchlorldes
the anhydrides.
This
the 4-phenoxy-
acetic
pyrldlne
anhydrlde
and
(and
dlmethyl-
acid solution.
9-12 --
ArTeC13
Base
5
NaOH
12
9
92
205-210
6
NaOH
12
ro
96
275-279
7
Na2C03
2
”
71
a
Na2C03
2
-12
96
Reaction Time (h)
2319
2
the corresponding
For example,
comparable
examihed
by reacting to give
afforded
dimethylfotmamide,
of Aryltellurlnlc
and
hydroxylamlne
their
They
in the
functionality
sodium hydroxide
spontaneously
oxidants.’ even
been known
11 were
tellurium
in most organic
In solvents
of 11 was,
1.
2 through
with aqueous
11 which
is scarcely
have
although
like the corresponding
0 with
and
or -NH-OH
We now report
anhydrides
to
hydrazlde
-NH-NH
investigated,
compounds 1 through
11 is only
sulphoxide.
little
selective
to qulnones
smoothly
acids and anhydrldes
acids 2 through
its congeners)
hydrarine,
appropriate
been
oxldising
class of compounds
converted
Is well known.
Treatment
are useful,
and catechols
are
The
that
Organotellurinic chemical
and its congeners
hydroqulnones
206-205
3
273-275
276
3
230-235
230
3
D. H. R. BARKIN er al.
2320
Phenols in
refluxlng
(2,5-dl-tort.-butylphenol and 3,5-dl-tort.-butylphenol) acid, even after 7 days, and were recovered in
acetic
Hydroqulnones
were
1.4~benzoqulnone temperature
easily
oxldlsed
4-phenylurazole
corresponding 88%).
5 days.
was obtained
The
after
24 hrs.
48 hrs,
Substrate
Reaction
were smoothly 86%),
oxldlsed
converted
at room
dl-(4-tort.-butyl-2-
g-phthaloylhydrazlde acetate
Is performed
E
as trapplng
and
agent,
after
of 11 with
to the thloester
In DMF at 1 loo,
30
only
(54%) in
27% of 30
Hydroqulnone
Product
and Thlols
Yliy
Lit.
i!$p*
lZ.5’
80
1
84
-16
95
150-152
150-151
-17 -19
20
3
56
121-122
125
9
18
83
-18 -20
81
20
86
58-60
61
10
z
20
20
88
22
94
61-63
thlophenol
to assess the relative were
2J.
appeared the ratlo
In order reactions
that
The
performed
reactions
reaction
between
the reduced
tellurium
in 4 and
82% Instead
showed
( 70% In 15 min.)
that
Table
3.
-11 9
vs
-12
Wlth
2
occurred
Competition
11
anhydrldes
substrate
11 and 32 with
and telluroxldes,
(Table
46% respectively
After after
2
Tellurium
Reduced A
fi
Derlvatlves
To Reagents B
95
23
?!! -36
32
97
36 5
46
vs
-32 -11
vs
-32
96
37
33
-34
67
25 57 60
thlophencil
Oxidants vs
70
21 Ylld f Dlsufphl~e 12 I%1 98
90 mln.,
very
and dianlsyltelluroxlde
z
Ylld f O:no:e 18
and
However,
30 mlns.
by the anhydride
dltellurlde
wlth Various
3).
z
It
1,4-dihydroxynaphthalene,
was time-dependent.
was reoxldlsed between
Reactions
With 1,4-dlhydroxynaphthalene
Oxidants
of 32 and
8
: 1,4-dlhydroxynaphthaIene
In oxldlsed
between
compounds
dianlsyltellurlde
but no reaction
of tellurlnlc
two substrates
were quantitative
In the competition
recovered
experiments
reactlvlty
with
24
by 11 In acetic
-28.
Yield of [Ph-&C6H4Te),
Time lh)
(2,5-dl-tort.-butyl
27 were also unaffected
28 was slowly reaction
not oxldlsed yield.
15
competition
were
Temp. 1°C)
conditions,
with ergosteryl
with 39% unreacted
2.
Thlophenols
26 and lndollne
If the
qulnones
(dlphenyldlsulphlde
these
S-methylxanthate
Table
2
81%).
Under
Pyrrolldlne
acid at 1 loo for
corresponding
dlsulphldes
20 did not give any adduct
hrs at room temperature. acid for
the
95%. 1,4_naphthoqulnone
to the
methylphenyl)dlsulphide
acetic
to
were 90-95%
-11 9
-32 -11
92
36 35
68
vs
19
-34 -36
11
vs
-32
95
-37
1
-34
‘,
and
Blank quickly 2.
&ganotcUurinic acid anhydridcsas s&c!ivc oxidantsin or&c To avoid reactivitles
any
were eventually
side
reaction
between
determined
on Z,S-di-tort.-butyl-1,4_hydroquinone order
shows that
tellurlnlc
the different
by comparing Is,
anhydrldes
with
the
are generally
tellurium
oxidation four milder
oxidants
than
> -11. As these studies were performed in acetic acid, telluroxlde as its dlacetatc -33.’ In the reaction with 1,4-dihydroxynaphthalene showed similar activity. However, in the reaction with the xanthate
failed
to react
(99% yield)
In 18 hrs
at room temperature,
with -29 in CH2C12 or In acetic acid under
Table
4.
Comparative
Actlvlties
of Various
but
similar
the
the
performed
(Table
-2
CH2C12 gave 2
species,
reactions
reagents
2321
syathuis
4).
relative In parallel
The
telluro%ldes
32 was In fact in CH2CI2, 2,
reactivity
: 12 > 32 mtactlng
31 and 23
telluroxlde
32 In diacetate 33
telluroxlde
conditions.
Tellurium
Derivatives
with 2,5-dl-tort.-butyl-1,Fhydroquinone”
Oxldant
Yield
of
Qulnone
57
-11 -12
11
4
92
86
32
68
52
51
Ruction performed in acetic acid for 6 hrs at room temperature under an atmorphera of argon.
Further
Ar=
Te
(%I
2
a:
in progress
Reduced
16 ($)
studies
on the scope of the reactivity
and will be reported
+ OMe
-
of tellurinlc
$-Bu’
are now
OPh
\
-
ArH
1
2
ArTeC13
5
6
(ArTeO)20
9
-10
(Ar+e12
-35
OH
acid anhydrldes
In due course.
OH
xx> 00
4 8 -12 -37
OH
OH
0
2322
D. H. R.
0
0 bH
u
al.
0
OH
00
&RTON
0
1
@
0
0
0
0
SH
-21
U?ICONH)~
-25
lul
(G 0
H”
IL
-29
R=
-SPh
r
R =
-SPh 6
(0
TeX2
Me0
32 x2 = 0 2X
0
-26
J3P Me0
m
IIH”
0
Te
= OAC
EXPERIMENTAL bf.p.6 were determined with a Kofler hot etagc lpparatua and are uncorrected. Ww lpoctra were determinedfor lolutiouain deuteriochloroform with TMS a. iutemal etaudardon a Variaa K-M 360 apparatua. IP epectra were recorded on a Perkin-Klrer297 lpectrowter. U.V.
ware recorded on a Perkin-Elmer Lambda 5 UP-VI. Spectrophotomer.Hama spectra were recordedvith au MI X8-9 iuatrumeut. All lolveuta and reagent.were purifiedaud dried by under light preaaurewa. performeduein8 Merck ltaudard tochuiquea. Columu chromatography Ki.e.lS.160 (230-400muh). epectra
Syntheei.of Aryl TelluriumTrichloridea telluriumtrichlorideawar. preparedby reactionof Ania,l-4, naphth71-5and 4-phenor7phenyl-6 the lrometichydrocarbonand telluriumtetrachlorid.. 4-(n-Bu~)phenyZtiZZ&wn tr&M.oride S wae preparedb7 heating at 8O.C for 2 hr. a mixture of x-buto~henzene 1 (37.9 g) and telluriumtetrachlorid.(8.28 6) under an ltmoephereof argon. The reactionmixturewas evaporatedto dv... under reducedpreaaureand the raaiduc extractedby hot lcetonitril.and filteredthroughCalit.. After coolim6,2 vu obtaineda.
OrganotcUuriuic tid
brown cryetrle C10E13C130To
Syntheele
(8.03
6,
repairam
of
Aryl
C,
anhydrides us &kctivc oxidants in orgnnic synthesis
75X), r.p. 161-163’C 31.41; 8, 3.42; 0,
Tellurinic
(?ound: C. 31.24; 4.16; Cl, 27.82X).
8,
3.37;
0.
2323
4.40;
Cl,
27.69.
Anhydrfdce
Aniegl Telhdnia Anh@i& i : A 10X aqueour #odicn hydroqde lolutlom (100 ml) vae llwly added to a vigoroaely ltlrred lolutlon of 2 (5 6) in W (50 ml). The h.ixtnro rU ltirred at room temperature for 12 hre md then the W ua8 dietilled off. The coald coleurleee mixture wee ecidified vith 8cetlc lcid Rnd the precipltete $iltered and dried to afford 2 (3.60 6, 92X) es a white crietelline powder, m.p. 205-2lO.C (lit. 200-205.C). m/z 469 (M - 30). I-In-Butoxyl-phan#t T82Elacinia Anh@i& 0 vu yielded E (1.89 6, 98X) l e l uhite crietalline 4.45; 0. 13.60. C20E2605Te2 requires C. 39.92;
prepercd pouder, H. 4.36;
by the eeme procedure. m.p. 275-279.C (Found: 0, 13.301).
2 c,
(2.42 39.99;
g) 8.
P-Pheno~~htm~t TeZZlcFinic Anh#t%de 11 : A 10X aaueoue eodium carbonate solution (500 11) WU elavlp eided io e vigorously e-tirr.dzlatioD of i-phenoxypheuylte.llurlum trfcbloride 7 (27.2 The mixture we ltirred under reflux for 2 hrs and the TEV wae dizilled off. R) in TEP (275 ml). %e pricipitnte wee filtered from the cooled pture , veehed with Ii20 and dried in vacua to afford
-11 (15.38
2-h’@th&Z
(1.15
8,
Oxidetionr
g,
Tetlurinio 98X), m.p. with
71X).
m.p.
A*c?&& 230-235-C.
273-275%.
g lit.
4-Phenoxyphmyl
lit.
ree prepared 230-C.
tellurinic
276.C.
by the
Anbydride
eeme procedure
: 0 (1.5 6) yielded
12
fi
2, C-Di-tart. -butyZ-1, I-benwquirwne E : A rolutioa of 2,5-di-trrt.-butyl-l,4-hydraqoinone 15 (0.666 g)n acetic acid (5 ml) vae rlowly edded (15 mine) toxlution of 11 (0.705 6) ir The airture wee ltlrred for 1 hryt 80%. After acetic acid. under en ltmoephere of ergon. the reeidue vae lxtrected ulth CB Cl . The orSanic phue dietilletion under reduced preeeure, Colunn chromatogreph# (hueat: hex-e-toluene V&Y weehed vith E 0. 5X lqueoue Ha CO , and H 0. 2:3) lfforded d&4-phenoxyphenyl 36 (0.542 8, 84X) aa purple crgetale ?a i&lurid? (?=nd: C. 48.75; 8, 3.28; 0. 5.36. C H 0 Te2, (aethylenedichloride-ethanol), m.p. 93-95-C. H. 3.05; 0, 5.39X1, followed b# 16 (0.631 8, 95X) M orange c@+t requiree C, 48.56; (me~hplenedichloride-h-e); m.p. 150-152.C. lit. 150-15l.C: u_, (CItCl,) 1640 cm ; 6 (cDC13) 6.6 (2H. (I, 3-R and 6-E) and 1.3 (18 E. e, E.-f&). 1,4-Raphthoqui?wna ‘B : A oolution of 1.4-dlhydroxynephthalent E (0.160 6) VU added to l The mixture vae eolution of g (0.225 8) in acetic acid (3 ml), under an atmosphere of argon. Work-up l e above followed by column chrometogrephy stirred for 40 mine at room twereture. (eluant: toluene-hexene 7:3) afforded 36 (0.195 6, 98X) end92 (0.142 6, 89X) aa orenge 121-122-c; v (CHC13) 1670 cqftals (methylenedichloride-ethanol); m.p. 121-122.C. lit. (48. m. 5-H. 6-H. 7-H and 8-E). 7.25 (28, e, 2-E anby-8): x (EtOE) cm ; 6 (CDcl ) 8.5-7.9 mu. 319 (2500) ana 331.6 (17000). DiphtmyZdieulphido z : Thiophenol 19 (0.215 6) vae added to a rtirred eolutlon of fi (0.210 6) in lcetic ecid (2 ml). under an lGDher4 of erRon. The mixture wee etirred for 1 hr at room W&k-up-se lbove followid by colti chr_toSraphy yielded 20 (0.#4 temperature. 8, 86X) l e 61-C. and -36 colourlees, odorleee cryetele (methylenedlchloride-ethanol), m.p. 58-60%. lit. (0.167 6, 83X). Di(4-tert.-butl/2-2-meth~Zphm~ZMuuZphids 22 : 4-tert.-butyl-2-methylthiophenol 21 (0.350 8) we eddcd to .s eolutioa of 11 (0.213 P) ln%etica (2 ml) under a~ ltmoeDherrof nrRon. The mixture vu etirred for i hr a;. ram taper.&. U&k-up follcwed ‘by cot_ chrmntogrephy (eluunt: hexeee-ether 95:5) afforded 22 (0.340 6. 94X) l e colorless cryeta (methylenedichloride-•thenol); l .p. 63-65.C; Y (CRC1 ): no S-E band et 2550 g ; 6 (CDCl ) 7.35-7.20 (38, m, AM), 2.5 (38, e, CR ) end ly(9E, sb3tert.-butyl); m/z 358 @I ); [Pound: 3. II, 8.43X1. fxarad by z (0.173 6, 68X). 73.06; A. 0.50. C22H30S2 requires C. j3.68; sa-c?wZ43etu71-39-02 mnth~Zthicua&mt 30 : A mixture of _&ate 28 (0.233 8) end 11 (0.214 6) in lcetic ecld (IO ml) vae heeted for 24 hrs at llO*C under ~1 &bphere of.argony Work-up gradient) afforded 30 (0.122 6, 54X), m-p. ;; ;;gm c:;mffogreW (elurnt : ether-huene of di(4-pheooxyphenyl)~telluride end 117-C and a mixture di(4-phen&yphe~yl)telluride (0.087 6). When the ruction VU performed lo DlIp (10 ml) for 48 hre et llO*C. 30 (0.061 6, 27X) end e mixture of telluride and ditelluride (0.184 g) were recovered. Oxidetion
of S-Phenylxenthate
29 -*
4) With DianM~Z TeZZul~rfde : A mfxture of ranthate 2 (0.176 6) end dieaL+ telluroxide 2 (0.132 6) in CE Cl (10 ml) vRe etirred for 8 bre et room tapereture. Colurm chrometography (eluent : ether-#ex&e) afforded aflphur (0.012 6, 100X) thiocarbonatc 31 (0.167 6, 972); m.p. 125-128.C; v (CRC1 ) 1715 a; d (CDCl ) 7.85-7.35 (5E. I, Arll), c&3 (la, m. W/2 21 Ex. 3-E and 2.4??6 (46E?m. cbolertene); m/z $12 CM+>. 400 and 371. followed by 2 (0.107 6, b) with diwzi~ZteZZmxide diaaatuk 94X). : Similer reection ueing g (0.170 6) iaeteed of 32 Save ImchaISed 29 after 36 hre et room teupereture. Addition of pyrldine (0.5 ml) did not a) Wth 4-phenoq@~ZtrZZxrinio anhy&ida : A mixture of untbta 19 zdify the reaction.
D. H. R. BAIRN er ol.
2324
(0.176 g), fi thiocarbonata Capatition
(0.1 d 31, but Studlax
in acetic acid (2 ml) only unraacted -29.
atirrad
at
room taparatura
for
36 hra
gwa
no
:
CenezuZ B : Acetic acid (5 ml) vax addad to tha al WitJI 1,4-Dihydmqxuphthakna 17. mixture of E (0.160 8. 1 d) d-the fro orgenotellurium compound@, under en atmosphere of argon. Tha mixture vu ltirrd for 30 mine. at room taperature end than utractad vith methylanedichloride. Fe organic phaae vae vuhd vith vatar, 10% aquaoux NallCO end vetar, dried over *odium eulpheto and aveporeted under raduccd preeeura. Column chr o&a togWhY (ahtat: toluana-haxena 7:3) afforded the tvo raducad organotellurium compounda and g. I) 11 (0.250 8) aad 32 (0.403 6) SW. 36 (0.063 8, 42%). 34 (0.208 8, 56%) and 18 (0.139 S, 88%); ii) 9 (0.187 STend 11 (0.248 B)-i+e 35 (0.044 6, TX), 36 (0.128 6, 64Xrend 18 (0.151 6, 95x>: iii) 12 (0.2Org) and 21 (0.400-g) gave 37 (0.125 T, 73X), 2 (0.052 .g, ij%) and 2 (0.145 g, 9lZ bl vith I-Wt.-but& Z-methyZthiophenol 21. Genemt ~&UW : 21 (0.360 6) v.x addad to the solution one tvo orgenotellurium capounde in acatic acid (5 z) under en atrorphera of argon. The mixtura vae atirrad for 1 hr et roa tcrperatura and then vorkad up u above. ether-huane gradient) afforded the tvu raducad organotallurium Column chrowtography (aluent: I) 11 (0.230 g) and 32 (0.400 8) Swa 36 (0.132 g, 68%). 34 compound8 and the dixulphida 22. 71) 9 (0.190 g)=d 11 (0.236 8) g.va 35 (0.031 8, 19n; (0.091 8, 25%) and 22 (0.350 c98X); fiI> 12 (0.205 g)-md 32 (0.394 ,3)-&t 21. (0.002 6, a (0.114 8, 57%) md 22 (0.331 6, 92%); 1%). -34 (0.207 6, 60%) and -22 (0.341 6, 95%). Ge?Wrat Propertie ta&zr& 2,C-di-tert.-bu~Z-l,4-h~~quinae 16. of 2.5-dI-tert.-butyl-1,4--hparoquInona g (0.222 6) a of the lquiv.) under atmosphara of argon vex diarolved In lcatic acid (5 end thus axtractad with wthylana ml). Tha mixture vat otirrad for 6 hrx at room taparatura Tha organic phaaa vae va&ad vith vetar end evaporated under reduced prareure. dichloride. toluene-hexana 7:3) afforded the reduced tellurium cqound, Calm chromatogrepby (aluant: 2,5-dI-tart.-butyl-pquinoona 16 end 2,5-dI-u.-butyl-1,4-hydroquinone g. a) Oxidation with anixylt~rinic anhydride 9 gwe 16 (0.127 g, 57%). 21. (0.082 6, 51%) end 15 (0.056 g, 29%). b) Oxidation vith 4-phano~banyl~llurinIc anhydride 11 (0.236 6) gave 3670.013 6, 4%) end c) Oxidation vith 2-naphthyl talluriaic anhydride &TO.205 g) gffe z 16 (0.025 8, 11%). d) Oxidation vith dIanIxyltelluroxIde v.145 6, 86%). x (0.204 g, 92%) and E (0.006 g, 3%). -32 (0.394 6) &WC -16 (0.150 S, 68%). -34 (0.177 S, 52%) and -15 (0.027 8, 12%). Canpariea of Ozid
RoMtion of Dimi8yLtettluwride 32 @ith di-(4-pmhenyll-diteZZ& dIaniryltelluroxIda 32 (0.36 6) a di-(4-phanoxyphenyl)-dItallurIda of mathylanadichlori~ (1 ml) and acetic acid (5 ml) VU xtirrad T.1.c. monitoring of undar en ltmoxphara of argon. temperature. formation of dIanisyltallurIda -36.
36.A solution of 36 (6;162 g) In n mixture for 5 day8 at room the reaction shoved no
R&z&ion of I-Phm~henyi!-tetlurinio Anhydride 11 with Dixanieyltelluride 34.A xolution of 4-phanoxyphanyl tallurinic anhydride 11 (0.1 6) zd dIani~yltallurIde 2 (rlbl g) In acetic acid (5 ml) vae xtirrad for 15 min. z room temperature under an atmosphere of argon. Tha mixture vex than utractad vith mathylana dichloride, varhad vith vatcr and dried over Na SO ; 3:l) gwa the ditellurida 36 (&Oh column ch-togrephy (aluant : haxana-mathylanedichlorIde When the reaction VU stirred for 1 hr. dIani~yltal~Ida g, 68%) end traca muntn of 2. -34 diaappaarad completely (by t.1.c. examination). REFERENCES
1. 2. 3.
4. 5. 6. :: 9. 10. 11.
755 (1979); a, D.E.R. Barton, S.V. Ley and C.A. Maarholr. J. Cham. SOC. Cham. Cm.. 37, Suppl. 1, 213 (1981); S.V. Tatrehedron Latts. 2l, 1785 (1980); 2 dam, Tatreh&ron. Lay, Ann. Rap. Roy. Sot. Cham.. B. 233 m80). E.D.K. Drev, J. Cham. Sot., 560 (1929). licantini, Univ. Sao Paula, Pac. Piloeof. Cienc. Letran. Bol. Quti., N. Patrasnani~ 2, 75 (1359); Thea. Ahatr., 58. 11256a (1958); C. Vicentini. E. Giaxbrecht and L.K.R. K.J. Irgolic, The Organic ChemixtrP of Tellurium, Pitabo, Cham. Bar., 92, 40 n959); Gordon anfi breach, Nav York, 1974. and E. Kirachba nm C.T. Morgan and B.E. Kallatt, 1080 (1926); L. Keichtl -J. Chem. Sot., &, 523, 211 (1936). B. Khainboldt and C. Vicantini, Chem. 8ar.. ,9, 624 (1956). H.D.K. Drav. J. Chm. Sot., 223 (192a7. I.D. Sadakov and A.A. Haksimanko, Zh. Obech. Khia., 47. 2536 (1957). A. Gurevitach. &r.. 2, 2427 (1899). I. Eailbron, Dictionary of Organic Corpoundn. 4th Ed. Eyre and Spottj svooda , London, Vta 6. 2386 (19651. Ida, voi: 3;- 1279 (1965). mR. Barton, N.J. Cu~aum and S.V. Lay, J. Cha. Sot., Perkin I. 16 50 (198(11).
Vol. 41 No. 8, pp. 2319 to 2324.1986 in chal miti.
ORGANOTELLURINIC
ACID
Derek
ANHYDRIDES
H.R.
lnstltut
Barton,
AS SELECTIVE
Jean-Pierre
OXIDANTS
IN ORGANIC
Flnet and Martial
de Chlmle des Substances
Naturelles,
91190 Clf-sur-Yvette,
SYNTHESIS
Thomas
C.N.R.S.,
France
(Recekd in Frmux 6 Jammy 1966)
acid anhydrides have been compared lbr their Abstrvct - Sever01 aryltellurinlc oxldising properties in acetic acid. Very high yields of quinones and disulphides can be obtained under candltlons where phenols are not oxldlsed.
Dlanisyltelluroxide thiols
to disulphldes
phenols
or
formation often
and
amlnes.
Many
thlones
of a diaryltelluride.
oxidised,
provided
propertles
for example,
have
hydrazlne
mild and selective The ponding
aromatic
through
i.
aryltellurinlc
anhydride
agents
aryltellurinic
of the latter
and The
soluble
soluble
in acetic
on heating
reactivity
Table
acid (and
Synthesis
like
therefore,
ketones
that
other
for
aryltellurlnlc
oxldlse
presence
sulphur
of
wlth
functions
are
is present. some time. 283
reduction
Their
to ditellurides
by,
acid anhydrides
are
diaryltelluroxides. prepared
tetrachloride
lose water
to give
solvents.
aclds).
in acetic
Anhydrides
the corres-
the trlchlorldes
the anhydrides.
This
the 4-phenoxy-
acetic
pyrldlne
anhydrlde
and
(and
dlmethyl-
acid solution.
9-12 --
ArTeC13
Base
5
NaOH
12
9
92
205-210
6
NaOH
12
ro
96
275-279
7
Na2C03
2
”
71
a
Na2C03
2
-12
96
Reaction Time (h)
2319
2
the corresponding
For example,
comparable
examihed
by reacting to give
afforded
dimethylfotmamide,
of Aryltellurlnlc
and
hydroxylamlne
their
They
in the
functionality
sodium hydroxide
spontaneously
oxidants.’ even
been known
11 were
tellurium
in most organic
In solvents
of 11 was,
1.
2 through
with aqueous
11 which
is scarcely
have
although
like the corresponding
0 with
and
or -NH-OH
We now report
anhydrides
to
hydrazlde
-NH-NH
investigated,
compounds 1 through
11 is only
sulphoxide.
little
selective
to qulnones
smoothly
acids and anhydrldes
acids 2 through
its congeners)
hydrarine,
appropriate
been
oxldising
class of compounds
converted
Is well known.
Treatment
are useful,
and catechols
are
The
that
Organotellurinic chemical
and its congeners
hydroqulnones
206-205
3
273-275
276
3
230-235
230
3
D. H. R. BARKIN er al.
2320
Phenols in
refluxlng
(2,5-dl-tort.-butylphenol and 3,5-dl-tort.-butylphenol) acid, even after 7 days, and were recovered in
acetic
Hydroqulnones
were
1.4~benzoqulnone temperature
easily
oxldlsed
4-phenylurazole
corresponding 88%).
5 days.
was obtained
The
after
24 hrs.
48 hrs,
Substrate
Reaction
were smoothly 86%),
oxldlsed
converted
at room
dl-(4-tort.-butyl-2-
g-phthaloylhydrazlde acetate
Is performed
E
as trapplng
and
agent,
after
of 11 with
to the thloester
In DMF at 1 loo,
30
only
(54%) in
27% of 30
Hydroqulnone
Product
and Thlols
Yliy
Lit.
i!$p*
lZ.5’
80
1
84
-16
95
150-152
150-151
-17 -19
20
3
56
121-122
125
9
18
83
-18 -20
81
20
86
58-60
61
10
z
20
20
88
22
94
61-63
thlophenol
to assess the relative were
2J.
appeared the ratlo
In order reactions
that
The
performed
reactions
reaction
between
the reduced
tellurium
in 4 and
82% Instead
showed
( 70% In 15 min.)
that
Table
3.
-11 9
vs
-12
Wlth
2
occurred
Competition
11
anhydrldes
substrate
11 and 32 with
and telluroxldes,
(Table
46% respectively
After after
2
Tellurium
Reduced A
fi
Derlvatlves
To Reagents B
95
23
?!! -36
32
97
36 5
46
vs
-32 -11
vs
-32
96
37
33
-34
67
25 57 60
thlophencil
Oxidants vs
70
21 Ylld f Dlsufphl~e 12 I%1 98
90 mln.,
very
and dianlsyltelluroxlde
z
Ylld f O:no:e 18
and
However,
30 mlns.
by the anhydride
dltellurlde
wlth Various
3).
z
It
1,4-dihydroxynaphthalene,
was time-dependent.
was reoxldlsed between
Reactions
With 1,4-dlhydroxynaphthalene
Oxidants
of 32 and
8
: 1,4-dlhydroxynaphthaIene
In oxldlsed
between
compounds
dianlsyltellurlde
but no reaction
of tellurlnlc
two substrates
were quantitative
In the competition
recovered
experiments
reactlvlty
with
24
by 11 In acetic
-28.
Yield of [Ph-&C6H4Te),
Time lh)
(2,5-dl-tort.-butyl
27 were also unaffected
28 was slowly reaction
not oxldlsed yield.
15
competition
were
Temp. 1°C)
conditions,
with ergosteryl
with 39% unreacted
2.
Thlophenols
26 and lndollne
If the
qulnones
(dlphenyldlsulphlde
these
S-methylxanthate
Table
2
81%).
Under
Pyrrolldlne
acid at 1 loo for
corresponding
dlsulphldes
20 did not give any adduct
hrs at room temperature. acid for
the
95%. 1,4_naphthoqulnone
to the
methylphenyl)dlsulphide
acetic
to
were 90-95%
-11 9
-32 -11
92
36 35
68
vs
19
-34 -36
11
vs
-32
95
-37
1
-34
‘,
and
Blank quickly 2.
&ganotcUurinic acid anhydridcsas s&c!ivc oxidantsin or&c To avoid reactivitles
any
were eventually
side
reaction
between
determined
on Z,S-di-tort.-butyl-1,4_hydroquinone order
shows that
tellurlnlc
the different
by comparing Is,
anhydrldes
with
the
are generally
tellurium
oxidation four milder
oxidants
than
> -11. As these studies were performed in acetic acid, telluroxlde as its dlacetatc -33.’ In the reaction with 1,4-dihydroxynaphthalene showed similar activity. However, in the reaction with the xanthate
failed
to react
(99% yield)
In 18 hrs
at room temperature,
with -29 in CH2C12 or In acetic acid under
Table
4.
Comparative
Actlvlties
of Various
but
similar
the
the
performed
(Table
-2
CH2C12 gave 2
species,
reactions
reagents
2321
syathuis
4).
relative In parallel
The
telluro%ldes
32 was In fact in CH2CI2, 2,
reactivity
: 12 > 32 mtactlng
31 and 23
telluroxlde
32 In diacetate 33
telluroxlde
conditions.
Tellurium
Derivatives
with 2,5-dl-tort.-butyl-1,Fhydroquinone”
Oxldant
Yield
of
Qulnone
57
-11 -12
11
4
92
86
32
68
52
51
Ruction performed in acetic acid for 6 hrs at room temperature under an atmorphera of argon.
Further
Ar=
Te
(%I
2
a:
in progress
Reduced
16 ($)
studies
on the scope of the reactivity
and will be reported
+ OMe
-
of tellurinlc
$-Bu’
are now
OPh
\
-
ArH
1
2
ArTeC13
5
6
(ArTeO)20
9
-10
(Ar+e12
-35
OH
acid anhydrldes
In due course.
OH
xx> 00
4 8 -12 -37
OH
OH
0
2322
D. H. R.
0
0 bH
u
al.
0
OH
00
&RTON
0
1
@
0
0
0
0
SH
-21
U?ICONH)~
-25
lul
(G 0
H”
IL
-29
R=
-SPh
r
R =
-SPh 6
(0
TeX2
Me0
32 x2 = 0 2X
0
-26
J3P Me0
m
IIH”
0
Te
= OAC
EXPERIMENTAL bf.p.6 were determined with a Kofler hot etagc lpparatua and are uncorrected. Ww lpoctra were determinedfor lolutiouain deuteriochloroform with TMS a. iutemal etaudardon a Variaa K-M 360 apparatua. IP epectra were recorded on a Perkin-Klrer297 lpectrowter. U.V.
ware recorded on a Perkin-Elmer Lambda 5 UP-VI. Spectrophotomer.Hama spectra were recordedvith au MI X8-9 iuatrumeut. All lolveuta and reagent.were purifiedaud dried by under light preaaurewa. performeduein8 Merck ltaudard tochuiquea. Columu chromatography Ki.e.lS.160 (230-400muh). epectra
Syntheei.of Aryl TelluriumTrichloridea telluriumtrichlorideawar. preparedby reactionof Ania,l-4, naphth71-5and 4-phenor7phenyl-6 the lrometichydrocarbonand telluriumtetrachlorid.. 4-(n-Bu~)phenyZtiZZ&wn tr&M.oride S wae preparedb7 heating at 8O.C for 2 hr. a mixture of x-buto~henzene 1 (37.9 g) and telluriumtetrachlorid.(8.28 6) under an ltmoephereof argon. The reactionmixturewas evaporatedto dv... under reducedpreaaureand the raaiduc extractedby hot lcetonitril.and filteredthroughCalit.. After coolim6,2 vu obtaineda.
OrganotcUuriuic tid
brown cryetrle C10E13C130To
Syntheele
(8.03
6,
repairam
of
Aryl
C,
anhydrides us &kctivc oxidants in orgnnic synthesis
75X), r.p. 161-163’C 31.41; 8, 3.42; 0,
Tellurinic
(?ound: C. 31.24; 4.16; Cl, 27.82X).
8,
3.37;
0.
2323
4.40;
Cl,
27.69.
Anhydrfdce
Aniegl Telhdnia Anh@i& i : A 10X aqueour #odicn hydroqde lolutlom (100 ml) vae llwly added to a vigoroaely ltlrred lolutlon of 2 (5 6) in W (50 ml). The h.ixtnro rU ltirred at room temperature for 12 hre md then the W ua8 dietilled off. The coald coleurleee mixture wee ecidified vith 8cetlc lcid Rnd the precipltete $iltered and dried to afford 2 (3.60 6, 92X) es a white crietelline powder, m.p. 205-2lO.C (lit. 200-205.C). m/z 469 (M - 30). I-In-Butoxyl-phan#t T82Elacinia Anh@i& 0 vu yielded E (1.89 6, 98X) l e l uhite crietalline 4.45; 0. 13.60. C20E2605Te2 requires C. 39.92;
prepercd pouder, H. 4.36;
by the eeme procedure. m.p. 275-279.C (Found: 0, 13.301).
2 c,
(2.42 39.99;
g) 8.
P-Pheno~~htm~t TeZZlcFinic Anh#t%de 11 : A 10X aaueoue eodium carbonate solution (500 11) WU elavlp eided io e vigorously e-tirr.dzlatioD of i-phenoxypheuylte.llurlum trfcbloride 7 (27.2 The mixture we ltirred under reflux for 2 hrs and the TEV wae dizilled off. R) in TEP (275 ml). %e pricipitnte wee filtered from the cooled pture , veehed with Ii20 and dried in vacua to afford
-11 (15.38
2-h’@th&Z
(1.15
8,
Oxidetionr
g,
Tetlurinio 98X), m.p. with
71X).
m.p.
A*c?&& 230-235-C.
273-275%.
g lit.
4-Phenoxyphmyl
lit.
ree prepared 230-C.
tellurinic
276.C.
by the
Anbydride
eeme procedure
: 0 (1.5 6) yielded
12
fi
2, C-Di-tart. -butyZ-1, I-benwquirwne E : A rolutioa of 2,5-di-trrt.-butyl-l,4-hydraqoinone 15 (0.666 g)n acetic acid (5 ml) vae rlowly edded (15 mine) toxlution of 11 (0.705 6) ir The airture wee ltlrred for 1 hryt 80%. After acetic acid. under en ltmoephere of ergon. the reeidue vae lxtrected ulth CB Cl . The orSanic phue dietilletion under reduced preeeure, Colunn chromatogreph# (hueat: hex-e-toluene V&Y weehed vith E 0. 5X lqueoue Ha CO , and H 0. 2:3) lfforded d&4-phenoxyphenyl 36 (0.542 8, 84X) aa purple crgetale ?a i&lurid? (?=nd: C. 48.75; 8, 3.28; 0. 5.36. C H 0 Te2, (aethylenedichloride-ethanol), m.p. 93-95-C. H. 3.05; 0, 5.39X1, followed b# 16 (0.631 8, 95X) M orange c@+t requiree C, 48.56; (me~hplenedichloride-h-e); m.p. 150-152.C. lit. 150-15l.C: u_, (CItCl,) 1640 cm ; 6 (cDC13) 6.6 (2H. (I, 3-R and 6-E) and 1.3 (18 E. e, E.-f&). 1,4-Raphthoqui?wna ‘B : A oolution of 1.4-dlhydroxynephthalent E (0.160 6) VU added to l The mixture vae eolution of g (0.225 8) in acetic acid (3 ml), under an atmosphere of argon. Work-up l e above followed by column chrometogrephy stirred for 40 mine at room twereture. (eluant: toluene-hexene 7:3) afforded 36 (0.195 6, 98X) end92 (0.142 6, 89X) aa orenge 121-122-c; v (CHC13) 1670 cqftals (methylenedichloride-ethanol); m.p. 121-122.C. lit. (48. m. 5-H. 6-H. 7-H and 8-E). 7.25 (28, e, 2-E anby-8): x (EtOE) cm ; 6 (CDcl ) 8.5-7.9 mu. 319 (2500) ana 331.6 (17000). DiphtmyZdieulphido z : Thiophenol 19 (0.215 6) vae added to a rtirred eolutlon of fi (0.210 6) in lcetic ecid (2 ml). under an lGDher4 of erRon. The mixture wee etirred for 1 hr at room W&k-up-se lbove followid by colti chr_toSraphy yielded 20 (0.#4 temperature. 8, 86X) l e 61-C. and -36 colourlees, odorleee cryetele (methylenedlchloride-ethanol), m.p. 58-60%. lit. (0.167 6, 83X). Di(4-tert.-butl/2-2-meth~Zphm~ZMuuZphids 22 : 4-tert.-butyl-2-methylthiophenol 21 (0.350 8) we eddcd to .s eolutioa of 11 (0.213 P) ln%etica (2 ml) under a~ ltmoeDherrof nrRon. The mixture vu etirred for i hr a;. ram taper.&. U&k-up follcwed ‘by cot_ chrmntogrephy (eluunt: hexeee-ether 95:5) afforded 22 (0.340 6. 94X) l e colorless cryeta (methylenedichloride-•thenol); l .p. 63-65.C; Y (CRC1 ): no S-E band et 2550 g ; 6 (CDCl ) 7.35-7.20 (38, m, AM), 2.5 (38, e, CR ) end ly(9E, sb3tert.-butyl); m/z 358 @I ); [Pound: 3. II, 8.43X1. fxarad by z (0.173 6, 68X). 73.06; A. 0.50. C22H30S2 requires C. j3.68; sa-c?wZ43etu71-39-02 mnth~Zthicua&mt 30 : A mixture of _&ate 28 (0.233 8) end 11 (0.214 6) in lcetic ecld (IO ml) vae heeted for 24 hrs at llO*C under ~1 &bphere of.argony Work-up gradient) afforded 30 (0.122 6, 54X), m-p. ;; ;;gm c:;mffogreW (elurnt : ether-huene of di(4-pheooxyphenyl)~telluride end 117-C and a mixture di(4-phen&yphe~yl)telluride (0.087 6). When the ruction VU performed lo DlIp (10 ml) for 48 hre et llO*C. 30 (0.061 6, 27X) end e mixture of telluride and ditelluride (0.184 g) were recovered. Oxidetion
of S-Phenylxenthate
29 -*
4) With DianM~Z TeZZul~rfde : A mfxture of ranthate 2 (0.176 6) end dieaL+ telluroxide 2 (0.132 6) in CE Cl (10 ml) vRe etirred for 8 bre et room tapereture. Colurm chrometography (eluent : ether-#ex&e) afforded aflphur (0.012 6, 100X) thiocarbonatc 31 (0.167 6, 972); m.p. 125-128.C; v (CRC1 ) 1715 a; d (CDCl ) 7.85-7.35 (5E. I, Arll), c&3 (la, m. W/2 21 Ex. 3-E and 2.4??6 (46E?m. cbolertene); m/z $12 CM+>. 400 and 371. followed by 2 (0.107 6, b) with diwzi~ZteZZmxide diaaatuk 94X). : Similer reection ueing g (0.170 6) iaeteed of 32 Save ImchaISed 29 after 36 hre et room teupereture. Addition of pyrldine (0.5 ml) did not a) Wth 4-phenoq@~ZtrZZxrinio anhy&ida : A mixture of untbta 19 zdify the reaction.
D. H. R. BAIRN er ol.
2324
(0.176 g), fi thiocarbonata Capatition
(0.1 d 31, but Studlax
in acetic acid (2 ml) only unraacted -29.
atirrad
at
room taparatura
for
36 hra
gwa
no
:
CenezuZ B : Acetic acid (5 ml) vax addad to tha al WitJI 1,4-Dihydmqxuphthakna 17. mixture of E (0.160 8. 1 d) d-the fro orgenotellurium compound@, under en atmosphere of argon. Tha mixture vu ltirrd for 30 mine. at room taperature end than utractad vith methylanedichloride. Fe organic phaae vae vuhd vith vatar, 10% aquaoux NallCO end vetar, dried over *odium eulpheto and aveporeted under raduccd preeeura. Column chr o&a togWhY (ahtat: toluana-haxena 7:3) afforded the tvo raducad organotellurium compounda and g. I) 11 (0.250 8) aad 32 (0.403 6) SW. 36 (0.063 8, 42%). 34 (0.208 8, 56%) and 18 (0.139 S, 88%); ii) 9 (0.187 STend 11 (0.248 B)-i+e 35 (0.044 6, TX), 36 (0.128 6, 64Xrend 18 (0.151 6, 95x>: iii) 12 (0.2Org) and 21 (0.400-g) gave 37 (0.125 T, 73X), 2 (0.052 .g, ij%) and 2 (0.145 g, 9lZ bl vith I-Wt.-but& Z-methyZthiophenol 21. Genemt ~&UW : 21 (0.360 6) v.x addad to the solution one tvo orgenotellurium capounde in acatic acid (5 z) under en atrorphera of argon. The mixtura vae atirrad for 1 hr et roa tcrperatura and then vorkad up u above. ether-huane gradient) afforded the tvu raducad organotallurium Column chrowtography (aluent: I) 11 (0.230 g) and 32 (0.400 8) Swa 36 (0.132 g, 68%). 34 compound8 and the dixulphida 22. 71) 9 (0.190 g)=d 11 (0.236 8) g.va 35 (0.031 8, 19n; (0.091 8, 25%) and 22 (0.350 c98X); fiI> 12 (0.205 g)-md 32 (0.394 ,3)-&t 21. (0.002 6, a (0.114 8, 57%) md 22 (0.331 6, 92%); 1%). -34 (0.207 6, 60%) and -22 (0.341 6, 95%). Ge?Wrat Propertie ta&zr& 2,C-di-tert.-bu~Z-l,4-h~~quinae 16. of 2.5-dI-tert.-butyl-1,4--hparoquInona g (0.222 6) a of the lquiv.) under atmosphara of argon vex diarolved In lcatic acid (5 end thus axtractad with wthylana ml). Tha mixture vat otirrad for 6 hrx at room taparatura Tha organic phaaa vae va&ad vith vetar end evaporated under reduced prareure. dichloride. toluene-hexana 7:3) afforded the reduced tellurium cqound, Calm chromatogrepby (aluant: 2,5-dI-tart.-butyl-pquinoona 16 end 2,5-dI-u.-butyl-1,4-hydroquinone g. a) Oxidation with anixylt~rinic anhydride 9 gwe 16 (0.127 g, 57%). 21. (0.082 6, 51%) end 15 (0.056 g, 29%). b) Oxidation vith 4-phano~banyl~llurinIc anhydride 11 (0.236 6) gave 3670.013 6, 4%) end c) Oxidation vith 2-naphthyl talluriaic anhydride &TO.205 g) gffe z 16 (0.025 8, 11%). d) Oxidation vith dIanIxyltelluroxIde v.145 6, 86%). x (0.204 g, 92%) and E (0.006 g, 3%). -32 (0.394 6) &WC -16 (0.150 S, 68%). -34 (0.177 S, 52%) and -15 (0.027 8, 12%). Canpariea of Ozid
RoMtion of Dimi8yLtettluwride 32 @ith di-(4-pmhenyll-diteZZ& dIaniryltelluroxIda 32 (0.36 6) a di-(4-phanoxyphenyl)-dItallurIda of mathylanadichlori~ (1 ml) and acetic acid (5 ml) VU xtirrad T.1.c. monitoring of undar en ltmoxphara of argon. temperature. formation of dIanisyltallurIda -36.
36.A solution of 36 (6;162 g) In n mixture for 5 day8 at room the reaction shoved no
R&z&ion of I-Phm~henyi!-tetlurinio Anhydride 11 with Dixanieyltelluride 34.A xolution of 4-phanoxyphanyl tallurinic anhydride 11 (0.1 6) zd dIani~yltallurIde 2 (rlbl g) In acetic acid (5 ml) vae xtirrad for 15 min. z room temperature under an atmosphere of argon. Tha mixture vex than utractad vith mathylana dichloride, varhad vith vatcr and dried over Na SO ; 3:l) gwa the ditellurida 36 (&Oh column ch-togrephy (aluant : haxana-mathylanedichlorIde When the reaction VU stirred for 1 hr. dIani~yltal~Ida g, 68%) end traca muntn of 2. -34 diaappaarad completely (by t.1.c. examination). REFERENCES
1. 2. 3.
4. 5. 6. :: 9. 10. 11.
755 (1979); a, D.E.R. Barton, S.V. Ley and C.A. Maarholr. J. Cham. SOC. Cham. Cm.. 37, Suppl. 1, 213 (1981); S.V. Tatrehedron Latts. 2l, 1785 (1980); 2 dam, Tatreh&ron. Lay, Ann. Rap. Roy. Sot. Cham.. B. 233 m80). E.D.K. Drev, J. Cham. Sot., 560 (1929). licantini, Univ. Sao Paula, Pac. Piloeof. Cienc. Letran. Bol. Quti., N. Patrasnani~ 2, 75 (1359); Thea. Ahatr., 58. 11256a (1958); C. Vicentini. E. Giaxbrecht and L.K.R. K.J. Irgolic, The Organic ChemixtrP of Tellurium, Pitabo, Cham. Bar., 92, 40 n959); Gordon anfi breach, Nav York, 1974. and E. Kirachba nm C.T. Morgan and B.E. Kallatt, 1080 (1926); L. Keichtl -J. Chem. Sot., &, 523, 211 (1936). B. Khainboldt and C. Vicantini, Chem. 8ar.. ,9, 624 (1956). H.D.K. Drav. J. Chm. Sot., 223 (192a7. I.D. Sadakov and A.A. Haksimanko, Zh. Obech. Khia., 47. 2536 (1957). A. Gurevitach. &r.. 2, 2427 (1899). I. Eailbron, Dictionary of Organic Corpoundn. 4th Ed. Eyre and Spottj svooda , London, Vta 6. 2386 (19651. Ida, voi: 3;- 1279 (1965). mR. Barton, N.J. Cu~aum and S.V. Lay, J. Cha. Sot., Perkin I. 16 50 (198(11).