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The Reaction of iminosulfuranes with dimethyl acetylenedicarboxylate
TetrahedronLettersNo. 12, pp 1071 - 1074, 1974.
THE
Pergmon Press. Printed in Great Britain.
REACTION OF IMINOSZFUkVBS WITHDIMEIHX,ACETYIENEDICARHOXYLATE Y.Hayashi*,Y.Iwagami,A.Kadoi and T.Shono Departmentof SyntheticChemistry,Faculty of Engineering Kyoto University,Kyoto, Japan Daniel Stern Fels Research Instituteand Departmentof GhedstV Temple University,Philadelphia,Pennsylvania,19122
(Receivedin Japan 30 January 1974; received in UK for publication12 February1974)
Nmerous iminosulfuranes have been prepared122 but little has been done in exploring their syntheticapplications. In continuingstudies of the reactionof ylides with 1,3dipoles3,a new type of reactionwas found in the reaction of nitrile imines with N-carbeth0xyimincdimethylsulfurane.
R-o-C=N-NH-O-R'
+
Me2S=NCCOEt
Cl
R'=N02
Rm~-~,~o N
(I) a, R=H,
~
(II) IIIa, mp 352-355O,55% yield
b, R=CH3, R'=H
III&, mp 277-279: 40% yield
c, R=NO2, R'=H
IIIC~, mp 325-328:48% yield
0=I R' (III)
When nitrile imine precursor Ia was allowed to react with excess II in benzene at room twerature,
l-p-nitrophenyl-3-phenyl-l,2,4-triazollne-5-ohe was isolated.The structural
assignmentof the triazoloneIIIa was made on the basis of elementalanalysisand no depression of melting point on admixturewith an authenticspecimenpreparedby the method of Eksco and Musanto5. We assume that the reactionproceeds through initial formationof a sulfoniumsalt, which is subsequentlyhydrolyzedto III.
*
Present address:Departmentof Dyeing, Faculty of IndustrialArts, Kyoto Technical University,Matsugasaki,Kyoto, Japan 1071
1072
No. 12
Ar-C-N-SMe,
II C'O I&z
-HCl 1+11-
N\N/
Pt
II It
Ar-C-N-SMe-0Et
-2
111
H20
t
DMSO
------+ N\N/c=o
,
-
ir
Ar
Iminosu1furanescan be hydrolyzedto sulfoxideand amines as mentioned above.
Thktype
of hydrolysisis typical of phosphoniumsalts, affordingphosphineoxides and hydrocarbons, in contrastwith sulfoniumsalts which normally form sulfidesand alcohols'. Facile hydrolysisof the sulfoniumsalt suggeststhat this type of intermediatewould have similar propertiesto those of the (DMSO t DCC + H') system and, in the presence of 10 alcohols,alkoxysulfoniumsalts, intermediatesin the oxidationof alcohols , would be formed. That this is indeed the case was shown in the reactionof dimethylacetylenedicarboxylate with N-p-nitrophenyliminodimethylsulfurane (rVa) and an alcohol,as shown below. The reactionof sulfoniumylides with electrophilicacetylenesgives stable sulfonium ylides or furans6,7 . As we now show, iminosulties IV react with dimethyl acetylenedice boxylate and the products isolatedare dependenton reaction conditions. (a) -Reaction in a
Benzene ~
To a stirred solutionof IVa (0.01mol) in dry benzene, dimethylacetylenedicarboxylate(0.01mol) in benzene (2Cml)was added dropwise (2 hr) at room temperature and the mkture was stirred for an additionalten hours. The yellow precipitatewas filtered and recrystallizedfrom ethanol to yield VIIa (56%). The structureof the stable sulfoniumylide VIIa was substantiatedby elementalanalysis $+H16N206S); IR (Nujol),k=O
1728 and 1645cm-I;NMR (gin CIXl3), 3.11 (s, 6H), 3.60 (s, 3H),
3.70 (s, 3H), 6.91 (d, 2H), 8.12 (d, 2H). The formationof VII can be rationalizedas shown below:
cH302c\
CH302C, c_c/co2cH3 __,
t
/+-N-SMe2
,co2CH3
~_?
I
6r
L Ar-N=SMe2 (IV)
co
VIIa, Ar=p-N02C6Hy, mp 210-212", 56% yield V=b,
Ar= m-C1C6H4 ,
CH302c\
c--c
CH302C-C=C-C02CH3
mp 137-138°, 91% yield
WI)
(VII)
No. 12
1073
This mechanismis analogousto that reported for the reaction of LWSO with acetylenedicarboxylate8. (b) Reaction in Moist Solvents Treatmentof a moist chloroformsolutionof IVa with dimethylacetylenedicarboxylate was exothermicand affordeddknethylN-p-nitrophenylsminofumalate (iXa) quantitatively.Its structurewas based on the elementalanalysis,IR, NMR, Mass Spectra and comparisonwith an authenticspecimenpreparedby the method of Huisgenet al'. This reaction is so facile that the use of cornnercial undried solventsgives Ma as the main product.
cH302c\
CH302C-C=C-C02CH3 H2° +
-
"*3"2", c=c' ----+I\
C=CH-C02CH3 / N-8Me2 -OH
v-
,/"lH...
I
H
C-OCH o/ 3
i4r
Ar-N=SMe2
(VIII)
(Iv) IXa, Ar = p-N02C6H4,mp u8-11g”,
(IX)
100% yield
IXb, Ar = mN02C6H,,,mp gq-1010, 100% yield MC, Ar = CoOEt,
mp 24-26”)
(bp 132-@P/4
tor'r'), 100% yield
It is not immediatelyapparentwhen and how the streospecificformationof IX
OCCLES
and
speculationat this time is unwarranted9. when the reactionwas carried out in the presence of deuteriumoxide, the vinyl proton in Ma was completelyreplacedby deuterium. p-Nitrophenyliminohexadeuterodimethylsulfurane (IVa-D6)in moist chloroformgave lXa and hexadeuterodimethyl sulfoxide,results consistentwith the reactionmechanismdescribed. Reaction of II (hygroscopic) with dimethylacetylenedicarboxylate gave MC quantitatively (no reactionwas observedbetween urethane and dimethylacetylenedicarboxylate under the same conditions). (c) Reaction in the Fresenceof an Alcohol Oxidationof alcoholsto their correspondingcarbonylderivativeswith (DMSO t DCC + H') or (LMSO t anacid anhydride)" proceeds viyian oxysulfoniumsalt (X). Reaction of IVa with dimethylacetylenedicarboxylate in the presence of alcoholsgave csxbonylcompoundsin only fair yields, besides VIIa and Ma.
For example,oxidationof
@-phenylethylalcohol (0.01 mol) by the reagents (0.01molar solutionof each in benzene)
1074
No. 12
gave @-phenylethylalcohol (7081,8-phenylacetaldehyde (30%),Ma
(85%) and VIIa (5%).
Styrene could not be detectedin the reactionmixture by VPC (no eliminationreaction).
)=c! &Me,
/ /)=; + RCH2@I,
I Ar
N-SMe2
?,+,!3 H
F
I Ar
s
+
A _CCH*R
(V)
CH2R
(MI
03 FhCH20H
-
PhCH2CH20H -
PhCH2CH0,30% yield
Cyclohexanol-
Cyclohexanone,18% yield
n-Butanol
n-Butymldehyde, 15% yield
___)
RCHO +
CH3SG-13
PhCHO, 40% yield
Reaction in the presence of phenol gave o-msthylthionethylphenol in 15% yield. Although the yield of oxidationproduct is only fair and optimum conditionshave not been developed,This procedurehas a certsin advantageover other oxidationmethods since it proceeds under neutral conditions. Acknowledgement: The author (Y.H) is thankfulto professorsK.Te&nura and M.Ncxnura for their highly useful d.iscussions.
1. A.W.Johnson,"Ylid Chemistry",Academic Press (19661,p. 356. 2. H.Kise, G.Whitfieldand D.Swern, J. Org. Chem., z
1121 (1972)and references
cited therein. 3. Y.Hayashiand R.&la, TetrahedronLett., 605 (1970). 4. Initial product (yellcw-browncrystals,strong absorptionat 3320 and 1675 cm-') gave colorless111~ quantitativelywhen heated at 215-220'with evolutionof ethanol. 5. R.Fusco and C.Mussnto,Gazz. Chem. Ital., 68, 147 (1938). 6. M.T&sku, Y.Hayashiand H.Nozaki,TetrahedronLett., 2053 (1969). 7. M.Higo and TMukaiyama, m., 8. E.Winterfeldt, Chem. Her., 9,
2565 (1970). 1581 (1965).
ibid 9. R.Huisgen,H.Herbig,A.Siegel and H.Huber,_*,_,
99 2569 0966).
10. J.D.Albrightand L.Goldmsn,J. Amer. Chem. Sot., 87, 4214 (1965).
THE
Pergmon Press. Printed in Great Britain.
REACTION OF IMINOSZFUkVBS WITHDIMEIHX,ACETYIENEDICARHOXYLATE Y.Hayashi*,Y.Iwagami,A.Kadoi and T.Shono Departmentof SyntheticChemistry,Faculty of Engineering Kyoto University,Kyoto, Japan Daniel Stern Fels Research Instituteand Departmentof GhedstV Temple University,Philadelphia,Pennsylvania,19122
(Receivedin Japan 30 January 1974; received in UK for publication12 February1974)
Nmerous iminosulfuranes have been prepared122 but little has been done in exploring their syntheticapplications. In continuingstudies of the reactionof ylides with 1,3dipoles3,a new type of reactionwas found in the reaction of nitrile imines with N-carbeth0xyimincdimethylsulfurane.
R-o-C=N-NH-O-R'
+
Me2S=NCCOEt
Cl
R'=N02
Rm~-~,~o N
(I) a, R=H,
~
(II) IIIa, mp 352-355O,55% yield
b, R=CH3, R'=H
III&, mp 277-279: 40% yield
c, R=NO2, R'=H
IIIC~, mp 325-328:48% yield
0=I R' (III)
When nitrile imine precursor Ia was allowed to react with excess II in benzene at room twerature,
l-p-nitrophenyl-3-phenyl-l,2,4-triazollne-5-ohe was isolated.The structural
assignmentof the triazoloneIIIa was made on the basis of elementalanalysisand no depression of melting point on admixturewith an authenticspecimenpreparedby the method of Eksco and Musanto5. We assume that the reactionproceeds through initial formationof a sulfoniumsalt, which is subsequentlyhydrolyzedto III.
*
Present address:Departmentof Dyeing, Faculty of IndustrialArts, Kyoto Technical University,Matsugasaki,Kyoto, Japan 1071
1072
No. 12
Ar-C-N-SMe,
II C'O I&z
-HCl 1+11-
N\N/
Pt
II It
Ar-C-N-SMe-0Et
-2
111
H20
t
DMSO
------+ N\N/c=o
,
-
ir
Ar
Iminosu1furanescan be hydrolyzedto sulfoxideand amines as mentioned above.
Thktype
of hydrolysisis typical of phosphoniumsalts, affordingphosphineoxides and hydrocarbons, in contrastwith sulfoniumsalts which normally form sulfidesand alcohols'. Facile hydrolysisof the sulfoniumsalt suggeststhat this type of intermediatewould have similar propertiesto those of the (DMSO t DCC + H') system and, in the presence of 10 alcohols,alkoxysulfoniumsalts, intermediatesin the oxidationof alcohols , would be formed. That this is indeed the case was shown in the reactionof dimethylacetylenedicarboxylate with N-p-nitrophenyliminodimethylsulfurane (rVa) and an alcohol,as shown below. The reactionof sulfoniumylides with electrophilicacetylenesgives stable sulfonium ylides or furans6,7 . As we now show, iminosulties IV react with dimethyl acetylenedice boxylate and the products isolatedare dependenton reaction conditions. (a) -Reaction in a
Benzene ~
To a stirred solutionof IVa (0.01mol) in dry benzene, dimethylacetylenedicarboxylate(0.01mol) in benzene (2Cml)was added dropwise (2 hr) at room temperature and the mkture was stirred for an additionalten hours. The yellow precipitatewas filtered and recrystallizedfrom ethanol to yield VIIa (56%). The structureof the stable sulfoniumylide VIIa was substantiatedby elementalanalysis $+H16N206S); IR (Nujol),k=O
1728 and 1645cm-I;NMR (gin CIXl3), 3.11 (s, 6H), 3.60 (s, 3H),
3.70 (s, 3H), 6.91 (d, 2H), 8.12 (d, 2H). The formationof VII can be rationalizedas shown below:
cH302c\
CH302C, c_c/co2cH3 __,
t
/+-N-SMe2
,co2CH3
~_?
I
6r
L Ar-N=SMe2 (IV)
co
VIIa, Ar=p-N02C6Hy, mp 210-212", 56% yield V=b,
Ar= m-C1C6H4 ,
CH302c\
c--c
CH302C-C=C-C02CH3
mp 137-138°, 91% yield
WI)
(VII)
No. 12
1073
This mechanismis analogousto that reported for the reaction of LWSO with acetylenedicarboxylate8. (b) Reaction in Moist Solvents Treatmentof a moist chloroformsolutionof IVa with dimethylacetylenedicarboxylate was exothermicand affordeddknethylN-p-nitrophenylsminofumalate (iXa) quantitatively.Its structurewas based on the elementalanalysis,IR, NMR, Mass Spectra and comparisonwith an authenticspecimenpreparedby the method of Huisgenet al'. This reaction is so facile that the use of cornnercial undried solventsgives Ma as the main product.
cH302c\
CH302C-C=C-C02CH3 H2° +
-
"*3"2", c=c' ----+I\
C=CH-C02CH3 / N-8Me2 -OH
v-
,/"lH...
I
H
C-OCH o/ 3
i4r
Ar-N=SMe2
(VIII)
(Iv) IXa, Ar = p-N02C6H4,mp u8-11g”,
(IX)
100% yield
IXb, Ar = mN02C6H,,,mp gq-1010, 100% yield MC, Ar = CoOEt,
mp 24-26”)
(bp 132-@P/4
tor'r'), 100% yield
It is not immediatelyapparentwhen and how the streospecificformationof IX
OCCLES
and
speculationat this time is unwarranted9. when the reactionwas carried out in the presence of deuteriumoxide, the vinyl proton in Ma was completelyreplacedby deuterium. p-Nitrophenyliminohexadeuterodimethylsulfurane (IVa-D6)in moist chloroformgave lXa and hexadeuterodimethyl sulfoxide,results consistentwith the reactionmechanismdescribed. Reaction of II (hygroscopic) with dimethylacetylenedicarboxylate gave MC quantitatively (no reactionwas observedbetween urethane and dimethylacetylenedicarboxylate under the same conditions). (c) Reaction in the Fresenceof an Alcohol Oxidationof alcoholsto their correspondingcarbonylderivativeswith (DMSO t DCC + H') or (LMSO t anacid anhydride)" proceeds viyian oxysulfoniumsalt (X). Reaction of IVa with dimethylacetylenedicarboxylate in the presence of alcoholsgave csxbonylcompoundsin only fair yields, besides VIIa and Ma.
For example,oxidationof
@-phenylethylalcohol (0.01 mol) by the reagents (0.01molar solutionof each in benzene)
1074
No. 12
gave @-phenylethylalcohol (7081,8-phenylacetaldehyde (30%),Ma
(85%) and VIIa (5%).
Styrene could not be detectedin the reactionmixture by VPC (no eliminationreaction).
)=c! &Me,
/ /)=; + RCH2@I,
I Ar
N-SMe2
?,+,!3 H
F
I Ar
s
+
A _CCH*R
(V)
CH2R
(MI
03 FhCH20H
-
PhCH2CH20H -
PhCH2CH0,30% yield
Cyclohexanol-
Cyclohexanone,18% yield
n-Butanol
n-Butymldehyde, 15% yield
___)
RCHO +
CH3SG-13
PhCHO, 40% yield
Reaction in the presence of phenol gave o-msthylthionethylphenol in 15% yield. Although the yield of oxidationproduct is only fair and optimum conditionshave not been developed,This procedurehas a certsin advantageover other oxidationmethods since it proceeds under neutral conditions. Acknowledgement: The author (Y.H) is thankfulto professorsK.Te&nura and M.Ncxnura for their highly useful d.iscussions.
1. A.W.Johnson,"Ylid Chemistry",Academic Press (19661,p. 356. 2. H.Kise, G.Whitfieldand D.Swern, J. Org. Chem., z
1121 (1972)and references
cited therein. 3. Y.Hayashiand R.&la, TetrahedronLett., 605 (1970). 4. Initial product (yellcw-browncrystals,strong absorptionat 3320 and 1675 cm-') gave colorless111~ quantitativelywhen heated at 215-220'with evolutionof ethanol. 5. R.Fusco and C.Mussnto,Gazz. Chem. Ital., 68, 147 (1938). 6. M.T&sku, Y.Hayashiand H.Nozaki,TetrahedronLett., 2053 (1969). 7. M.Higo and TMukaiyama, m., 8. E.Winterfeldt, Chem. Her., 9,
2565 (1970). 1581 (1965).
ibid 9. R.Huisgen,H.Herbig,A.Siegel and H.Huber,_*,_,
99 2569 0966).
10. J.D.Albrightand L.Goldmsn,J. Amer. Chem. Sot., 87, 4214 (1965).