A facile synthesis of dispiro[indole-3,2′-pyrrolidine-3,5″-[1, 3]thiazolane] derivatives from 2,3,5-trisubstituted-4-thiazolidinones via 1,3-dipolar cycloaddition reaction

Article abstract of DOI:10.3184/174751914X13965156954070

A series of 2″,3″,4′-triaryl-1′- methyldispiro[indole-3,2′-pyrrolidine-3′,5″-[1,3]thiazolane] -2(1H),4″-dione derivatives were successfully synthesised via a three-component 1,3-dipolar cycloaddition reaction of 2,3,5-trisubstituted-4- thiazolidinones, is

Full text of DOI:10.3184/174751914X13965156954070

JOURNAL OF CHEMICAL RESEARCH 2014
VOL. 38 MAY, 283–286
RESEARCH PAPER 283
A facile synthesis of dispiro[indole-3,2′-pyrrolidine-3,5′′-[1,3]thiazolane]
derivatives from 2,3,5-trisubstituted-4-thiazolidinones via 1,3-dipolar
cycloaddition reaction
Guo-Liang Feng*, Hong-Li Zhang and Li-Jun Geng
School of Science, Hebei University of Science and Technology, Yuhua Road, Shijiazhuang 050018, P.R. China
A series of 2′′,3′′,4′-triaryl-1′-methyldispiro[indole-3,2′-pyrrolidine-3′,5′′-[1,3]thiazolane]-2(1H),4′′-dione derivatives were
successfully synthesised via a three-component 1,3-dipolar cycloaddition reaction of 2,3,5-trisubstituted-4-thiazolidinones,
isatin and sarcosine in refluxing toluene. Such a strategy would provide access to a fast one-pot synthesis of spiroheterocycle
in high yields.
Keywords: 2′′,3′′,4′-triaryl-1′-methyldispiro[indole-3,2′-pyrrolidine-3′,5′′-[1,3]thiazolane]-2(1H),4′′-dioneꢀꢀderivatives,ꢀ
2,3,5-trisubstituted-4-thiazolidinones,ꢀisatin,ꢀsarcosine,ꢀ1,3-dipolarꢀcycloadditionꢀreaction
Theꢀ 1,3-dipolarꢀ cycloaddition,ꢀ alsoꢀ knownꢀ asꢀ theꢀ Huisgenꢀ
cycloaddition,ꢀisꢀconsideredꢀtoꢀbeꢀoneꢀofꢀtheꢀmostꢀpowerfulꢀtoolsꢀ
forꢀtheꢀconstructionꢀofꢀaꢀvarietyꢀofꢀfive-memberedꢀheterocyclicꢀ
compoundsꢀ suchꢀ asꢀ pyrrolidines,ꢀ pyrrolinesꢀ andꢀ pyrroles.1,2ꢀ
Theseꢀ strategiesꢀ offerꢀ significantꢀ advantagesꢀ overꢀ traditionalꢀ
approaches,ꢀallowingꢀforꢀtheꢀconstructionꢀofꢀcomplexꢀmolecularꢀ
architecturesꢀfromꢀeasilyꢀavailableꢀstartingꢀmaterialsꢀinꢀaꢀsingleꢀ
operationꢀwithoutꢀtheꢀneedꢀforꢀtheꢀisolationꢀofꢀintermediates.
Theꢀ azomethineꢀ ylides,ꢀ whichꢀ areꢀ zwitterionicꢀ andꢀ areꢀ
composedꢀ ofꢀ oneꢀ positivelyꢀ chargedꢀ nitrogenꢀ atomꢀ andꢀ twoꢀ
terminalꢀsp2-hybridisedꢀcarbonꢀatoms,ꢀareꢀaꢀclassꢀofꢀpowerfulꢀ
reagentsꢀusedꢀinꢀ1,3-dipolarꢀcycloadditionꢀreactions.ꢀTherefore,ꢀ
Recently,ꢀ weꢀ describedꢀ aꢀ newꢀ andꢀ efficientꢀ syntheticꢀ
methodꢀofꢀspiropyrrolidineꢀderivativesꢀviaꢀaꢀthree-componentꢀ
1,3-dipolarꢀcycloadditionꢀreaction.15ꢀAsꢀaꢀpartꢀofꢀownꢀinterestꢀ
inꢀ cycloadditionꢀ reactions,ꢀ weꢀ reportꢀ hereꢀ forꢀ theꢀ firstꢀ timeꢀ
theꢀ synthesisꢀ ofꢀ novelꢀ 2′′,3′′,4-triaryl-1′-methyldispiro[indole-
3,2′-pyrrolidine-3′,5′′-[1,3]thiazolane]-2(1H),4′′-dioneꢀ
derivativesꢀviaꢀtheꢀone-pot,ꢀthree-componentꢀcondensationꢀofꢀ
2,3,5-trisubstituted-4-thiazolidinones,ꢀ isatinꢀ andꢀ sarcosineꢀ inꢀ
refluxingꢀtolueneꢀ(Schemeꢀ1).
Toꢀ achieveꢀ thisꢀ goal,ꢀ theꢀ startingꢀ compoundꢀ 2,3-diaryl-
4-thiazolidinonesꢀ wasꢀ preparedꢀ accordingꢀ toꢀ theꢀ procedureꢀ
describedꢀ byꢀ Srivastavaꢀ et al.16ꢀ byꢀ DCCꢀ mediatedꢀ three-
componentꢀ reactionꢀ ofꢀ amine,ꢀ aldehydeꢀ andꢀ mercaptoaceticꢀ
acid.ꢀ 2,3-Diaryl-5-arylmethylene-4-thiazolidinonesꢀ wasꢀ
preparedꢀ byꢀ theꢀ reactionꢀ ofꢀ 2,3-diaryl-4-thiazolidinonesꢀ andꢀ
aldehydeꢀinꢀEtOHꢀwithꢀNaOEtꢀasꢀtheꢀcatalystꢀ(Schemeꢀ2).17ꢀ1Hꢀ
NMRꢀspectraꢀofꢀ2,3-diaryl-5-arylmethylene-4-thiazolidinonesꢀ
1a–k displayedꢀaꢀsingletꢀatꢀaboutꢀ6.22ꢀppmꢀwhichꢀwasꢀassignedꢀ
toꢀaꢀCHꢀunit.ꢀAlso,ꢀtheꢀsignalsꢀofꢀE-isomersꢀwereꢀnotꢀobservedꢀ
inꢀtheꢀ1HꢀNMRꢀdata,ꢀtheꢀC=CHꢀofꢀ2,ꢀ3-diaryl-5-arylmethylene-
4-thiazolidinonesꢀwasꢀtheꢀformationꢀofꢀZ-isomers.18
theyꢀ affordꢀ aꢀ rangeꢀ ofꢀ importantꢀ heterocyclicꢀ compounds.3–5
ꢀ
Spiroheterocyclesꢀ representꢀ anꢀ importantꢀ classꢀ ofꢀ naturallyꢀ
occurringꢀsubstancesꢀcharacterisedꢀbyꢀtheirꢀhighlyꢀpronouncedꢀ
biologicalꢀ activities.ꢀ Recently,ꢀ someꢀ spiropyrrolidinesꢀ haveꢀ
receivedꢀ considerableꢀ attentionꢀ becauseꢀ ofꢀ theirꢀ potentialꢀ
applicationꢀ inꢀ theꢀ fieldsꢀ ofꢀ antileukaemic,6ꢀ anticonvulsantꢀ
agents,7ꢀ localꢀ anaestheticꢀ activities8ꢀ asꢀ wellꢀ asꢀ antiviral.9ꢀ Inꢀ
addition,ꢀoxindoleꢀderivativesꢀatꢀC3ꢀasꢀspirocarbo-ꢀhaveꢀservedꢀ
asꢀpotentialꢀsyntheticꢀintermediatesꢀforꢀbiologicalꢀapplicationsꢀ
suchꢀ asꢀ anti-fungal,ꢀ anti-mycobacterial,ꢀ anti-microbial,ꢀ anti-
malarialꢀandꢀothers.10–14
Toꢀ improveꢀ theꢀ yield, weꢀ investigatedꢀ theꢀ solventꢀ impactꢀ
onꢀtheꢀreactionꢀforꢀtheꢀsynthesisꢀofꢀcompoundꢀ4a.ꢀTheꢀresultsꢀ
Ar3
CH3
O
N
HN
O
S
Toluene
CH3NHCH2COOH
O
S
Ar1
O
Ar3
Refluxing
N
Ar2
N
Ar1
O
H
N
Ar2
1
2
3
4
Scheme 1
Ar3
S
S
EtONa
O
THF
Ar2NH2
Ar1CHO
Ar1
Ar1
O
HSCH2COOH
Ar3CHO
N
Ar2
N
DCC
Ar2
1
Scheme 2
* Correspondent.ꢀE-mail:ꢀfgl126hao@126.com

284ꢀꢀꢀJOURNALꢀOFꢀCHEMICALꢀRESEARCHꢀ2014
Table 1 Solvent optimisation for the synthesis of 4a
Theꢀ structuresꢀ ofꢀ theꢀ compoundsꢀ 4a–kꢀ wereꢀ fullyꢀ
characterisedꢀandꢀsupportedꢀbyꢀIR,ꢀ1HꢀNMRꢀandꢀelementaryꢀ
analysis.ꢀ Takingꢀ compoundꢀ 4a,ꢀ forꢀ example,ꢀ theꢀ peaksꢀ atꢀ
1729ꢀcm–1ꢀ andꢀ 1682ꢀcm–1ꢀ wereꢀ rationallyꢀ attributedꢀ toꢀ theꢀ
vibrationꢀ ofꢀ theꢀ isatinꢀ andꢀ thiazolidinoneꢀ ringꢀ carbonyls,ꢀ
respectivelyꢀinꢀtheꢀIRꢀspectrum.ꢀInꢀtheꢀ1HꢀNMRꢀspectrumꢀofꢀ
4a,ꢀtheꢀ–NHꢀprotonꢀexhibitedꢀaꢀsingletꢀatꢀδꢀ10.69.ꢀTheꢀ–NCH3ꢀ
protonsꢀofꢀtheꢀpyrrolidineꢀexhibitedꢀaꢀsingletꢀatꢀδꢀ2.09.
Basedꢀ onꢀ theꢀ aboveꢀ results,ꢀ theꢀ reactionꢀ mechanismꢀ wasꢀ
proposedꢀ asꢀ followsꢀ (Schemeꢀ 3).ꢀ Theꢀ isatinꢀ 2ꢀ reactedꢀ withꢀ
sarcosineꢀ 3ꢀ toꢀ giveꢀ intermediateꢀ 5ꢀ whichꢀ underwentꢀ heat-
promotedꢀ decarboxylation,ꢀ resultingꢀ inꢀ theꢀ formationꢀ ofꢀ theꢀ
azomethineꢀylidesꢀ6.ꢀ1,3-Dipolarꢀcycloadditionꢀofꢀ2,3-diaryl-
5-arylmethylene-4-thiazolidinonesꢀ 1ꢀ withꢀ azomethineꢀ ylidesꢀ
Entry
Solvent
1,4-Dioxane
Glycol monomethyl ether
Ethanol
Ethylene glycol
Acetonitrile
Methanol
Yield/%a
1
2
3
4
5
6
7
8
23
35
53
68
65
52
70
82
Benzene
Toluene
aIsolated yield.
wereꢀsummarisedꢀinꢀTableꢀ1.ꢀTheꢀreactionsꢀinꢀtheꢀsolventꢀofꢀ
1,4-dioxane,ꢀglycolꢀmonomethylꢀetherꢀgaveꢀlittleꢀofꢀtheꢀdesiredꢀ
product.ꢀ Whenꢀ theꢀ reactionsꢀ wereꢀ carriedꢀ outꢀ inꢀ ethanol,ꢀ
methanol,ꢀethyleneꢀglycol,ꢀacetonitrileꢀorꢀbenzene,ꢀcompoundꢀ
4aꢀ wasꢀ obtainedꢀ inꢀ moderateꢀ yieldsꢀ (Tableꢀ 1,ꢀ entriesꢀ 3–7).ꢀ
Surprisingly,ꢀtheꢀreactionꢀproceededꢀbestꢀinꢀtolueneꢀtoꢀgiveꢀaꢀ
goodꢀ82%ꢀyieldꢀ(Tableꢀ1,ꢀentryꢀ8).
Toꢀ extendꢀ theꢀ scopeꢀ ofꢀ thisꢀ newꢀ procedureꢀ forꢀ theꢀ
synthesisꢀ ofꢀ 2′′,3′′,4′-triaryl-1′-methyldispiro[indole-3,2′-
pyrrolidine-3′,5′′-[1,3]thiazolane]-2(1H),4′′-dione,ꢀ aꢀ seriesꢀ
ofꢀ analogousꢀ reactionsꢀ wereꢀ carriedꢀ outꢀ inꢀ toluene.ꢀ Theseꢀ
reactionsꢀproceededꢀsmoothlyꢀandꢀtheꢀdesiredꢀproductsꢀwereꢀ
affordedꢀ inꢀ excellentꢀ yields.ꢀ Notably,ꢀ theꢀ electronicꢀ effectsꢀ
ofꢀ theꢀ substituentꢀ onꢀ theꢀ aromaticꢀ ringꢀ haveꢀ noꢀ significantꢀ
influenceꢀonꢀtheꢀreactionꢀyieldsꢀ(Tableꢀ2).
6ꢀ
producedꢀ
2′′,3′′,4′-triaryl-1′-methyldispiro[indole-3,2-
pyrrolidine-3′,5′′-[1,3]thiazolane]-2(1H),4′′-dioneꢀderivativesꢀ4.
Conclusions
Inꢀsummary,ꢀaꢀnumberꢀofꢀinterestingꢀandꢀnovelꢀ2′′,3′′,4′-triaryl-
1′-methyldispiro[indole-3,2′-pyrrolidine-3,5′′-[1,3]thiazolane]-
2(1H),4′′-dioneꢀ derivativesꢀ startingꢀ fromꢀ 2,3-diaryl-5-
arylmethylene-4-thiazolidinonesꢀ byꢀ 1,3-dipolarꢀ cycloadditionꢀ
reactionꢀwereꢀpreparedꢀandꢀareꢀcharacterisedꢀinꢀthisꢀpaper.
Experimental
Meltingꢀ pointsꢀ wereꢀ recordedꢀ onꢀ anꢀ electrothermalꢀ digitalꢀ meltingꢀ
pointꢀapparatusꢀandꢀuncorrected.ꢀ1HꢀNMRꢀspectraꢀwereꢀdeterminedꢀ
onꢀaꢀVarianꢀVXP-500sꢀspectrometerꢀusingꢀDMSOꢀorꢀCDCl3ꢀasꢀsolventꢀ
Table 2 Three-component synthesis of dispiro[indole-3,2′-pyrrolidine-3′,5′′-[1,3]thiazolane] derivatives
Entry
Ar1
Ar2
Ar3
Producta
Yield/%b
M. p./°C
1
2
3
4
5
6
7
8
9
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
4-CH(CH3)2C6H4
4-CH(CH3)2C6H4
4-CH(CH3)2C6H4
4-CH(CH3)2C6H4
4-ClC6H4
C6H5
4-CH3C6H4
4-CH(CH3)2C6H4
4-C(CH3)3C6H4
C6H5
4a
4b
4c
4d
4e
4f
4g
4h
4i
82
80
84
82
79
81
76
80
76
78
82
225–226.6
234–235.6
218.4–220
234.3–235.4
240–241.2
152
4-CH3C6H4
4-CH(CH3)2C6H4
4-C(CH3)3C6H4
C6H5
4-CH3C6H4
4-CH(CH3)2C6H4
226.1
233.6–234.9
195.3–196.7
231.5–233.3
226.4–228
4-CH3C6H4
4-CH3C6H4
4-CH3C6H4
10
11
4-ClC6H4
4-ClC6H4
4j
4k
aThe products were characterised by 1H NMR, IR and elementary analysis.
bIsolated yield.
O
O
O
O
O
H3C
N
N
CH3
CH3NHCH2COOH
O
O
O
N
N
H
N
H
H
5
2
3
_
CO2
Ar3
CH3
CH3
N
N
S
HN
O
Ar1
O
N
Ar2
O
S
Ar3
O
NH
Ar1
N
Ar2
1
6
4
Scheme 3 A possible mechanism for synthesis of dispiro[indole-3,2′-pyrrolidine-3′,5′′-[1,3]thiazolane].

JOURNALꢀOFꢀCHEMICALꢀRESEARCHꢀ2014ꢀꢀꢀ285
andꢀ tetramethylsilaneꢀ (TMS)ꢀ asꢀ internalꢀ reference.ꢀ IRꢀ Spectraꢀ wasꢀ
obtainedꢀ onꢀ aꢀ Nicoletꢀ 6700ꢀ spectrophotometerꢀ usingꢀ KBrꢀ pellets.ꢀ
Elementaryꢀ analysesꢀ wereꢀ performedꢀ byꢀ aꢀ Carlo-Erbaꢀ EA1110ꢀ
CNNO–Sꢀanalyser.
Theꢀ generalꢀ procedureꢀ forꢀ theꢀ synthesisꢀ ofꢀ 2,3-diaryl-5-
arylmethylene-4-thiazolidinonesꢀ (1a–k) wasꢀ takenꢀ fromꢀ theꢀ
literature.16,17
(Z)-2-(4-Methylphenyl)-3-(4-chlorophenyl)-5-(4-methylphenyl-
methylene)-4-thiazolidinone (1j):ꢀ M.p.ꢀ 204.6−205.7ꢀ°C;ꢀ yieldꢀ 79%.ꢀ
IR(KBr):ꢀ 3030,ꢀ 2924,ꢀ 1666,ꢀ 1595,ꢀ 1492ꢀcm–1.ꢀ 1Hꢀ NMRꢀ (500ꢀMHz,ꢀ
CDCl3):ꢀδꢀ7.67ꢀ(s,ꢀ1H),ꢀ7.52ꢀ(d,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ7.42ꢀ(t,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ
7.30−7.18ꢀ(m,ꢀ6H),ꢀ7.10ꢀ(d,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ6.21ꢀ(s,ꢀ1H),ꢀ2.49ꢀ(s,ꢀ3H),ꢀ2.30ꢀ
(s,ꢀ3H).ꢀAnal.ꢀcalcdꢀforꢀC24H20ClNOS:ꢀC,ꢀ71.01;ꢀH,ꢀ4.97;ꢀN,ꢀ3.45;ꢀfound:ꢀ
C,ꢀ70.93;ꢀH,ꢀ5.06;ꢀN,ꢀ3.49%.
(Z)-2-(4-Methylphenyl)-3-(4-chlorophenyl)-5-(4-isopropylphenyl-
methylene)-4-thiazolidinone (1k): M.p. 223.5−224.7ꢀ°C;ꢀ yieldꢀ 80%.ꢀ
IR(KBr):ꢀ 3028,ꢀ 2926,ꢀ 1665,ꢀ 1597,ꢀ 1493ꢀcm–1.ꢀ 1Hꢀ NMRꢀ (500ꢀMHz,ꢀ
CDCl3):ꢀδꢀ7.66ꢀ(s,ꢀ1H),ꢀ7.54ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.0ꢀHz),ꢀ7.42ꢀ(t,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ
7.33−7.20ꢀ(m,ꢀ6H),ꢀ7.12ꢀ(d,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ6.22ꢀ(s,ꢀ1H),ꢀ2.96−2.89ꢀ(m,ꢀ
1H),ꢀ2.30ꢀ(s,ꢀ3H),ꢀ1.25ꢀ(d,ꢀ6H,ꢀJ=ꢀ7.0ꢀHz).ꢀAnal.ꢀcalcdꢀforꢀC26H24ClNOS:ꢀ
C,ꢀ71.95;ꢀH,ꢀ5.57;ꢀN,ꢀ3.23;ꢀfound:ꢀC,ꢀ71.86;ꢀH,ꢀ5.69;ꢀN,ꢀ3.17%.
(Z)-2,3-Diphenyl-5-phenylmethylene-4-thiazolidinone (1a):ꢀ M.p.ꢀ
191.5−192.3ꢀ°C;ꢀyieldꢀ84%.ꢀIR(KBr):ꢀ3034,ꢀ2928,ꢀ 1666,ꢀ1595,ꢀ1489,ꢀ
1442ꢀcm–1.ꢀ1HꢀNMRꢀ(500ꢀMHz,ꢀCDCl3):ꢀδꢀ7.69ꢀ(s,ꢀ1H),ꢀ7.55ꢀ(d,ꢀ2H,ꢀ
J=ꢀ7.5ꢀHz),ꢀ7.41ꢀ(t,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ 7.32−7.24ꢀ(m,ꢀ10H),ꢀ7.19−7.15ꢀ(m,ꢀ
1H),ꢀ6.27ꢀ(s,ꢀ1H).ꢀAnal.ꢀcalcdꢀforꢀC22H17NOS:ꢀC,ꢀ76.94;ꢀH,ꢀ4.99;ꢀN,ꢀ4.08;ꢀ
found:ꢀC,ꢀ76.87;ꢀH,ꢀ5.06;ꢀN,ꢀ4.01%.
(Z)-2,3-Diphenyl-5-(4-methylphenylmethylene)-4-thiazolidinone
(1b):ꢀ M.p.ꢀ 208.2−209.3ꢀ°C;ꢀ yieldꢀ 85%.ꢀ IR(KBr):ꢀ 3053,ꢀ 3024,ꢀ 2930,ꢀ
1662,ꢀ 1593,ꢀ 1493ꢀcm–1.ꢀ 1Hꢀ NMRꢀ (500ꢀMHz,ꢀ CDCl3):ꢀ δꢀ 7.66ꢀ (s,ꢀ 1H),ꢀ
7.37−7.23ꢀ(m,ꢀ12H),ꢀ7.19−7.16ꢀ(m,ꢀ1H),ꢀ7.12ꢀ(d,ꢀ1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ6.27ꢀ(s,ꢀ
1H),ꢀ2.37ꢀ(s,ꢀ3H).ꢀAnal.ꢀcalcdꢀforꢀC23H19NOS:ꢀC,ꢀ77.28;ꢀH,ꢀ5.36;ꢀN,ꢀ3.92;ꢀ
found:ꢀC,ꢀ77.36;ꢀH,ꢀ5.40;ꢀN,ꢀ3.78%.
(Z)-2,3-Diphenyl-5-(4-isopropylphenylmethylene)-4-thiazolidinone
(1c):ꢀ M.p.ꢀ 236.5−237.8ꢀ°C;ꢀ yieldꢀ 80%.ꢀ IR(KBr):ꢀ 3043,ꢀ 2960,ꢀ 1668,ꢀ
1595,ꢀ1494,ꢀ1456ꢀcm–1.ꢀ1HꢀNMRꢀ(500ꢀMHz,ꢀCDCl3):ꢀδꢀ7.67ꢀ(s,ꢀ1H),ꢀ7.48ꢀ
(d,ꢀ2H,ꢀJ=ꢀ8.0ꢀHz),ꢀ7.32−7.24ꢀ(m,ꢀ11H),ꢀ7.19−7.16ꢀ(m,ꢀ1H),ꢀ6.26ꢀ(s,ꢀ1H),ꢀ
2.96−2.88ꢀ(m,ꢀ1H),ꢀ1.25ꢀ(d,ꢀ6H,ꢀJ=ꢀ7.0ꢀHz).ꢀAnal.ꢀcalcdꢀforꢀC25H23NOS:ꢀ
C,ꢀ77.89;ꢀH,ꢀ6.01;ꢀN,ꢀ3.63;ꢀfound:ꢀC,ꢀ77.83;ꢀH,ꢀ5.92;ꢀN,ꢀ3.75%.
( Z)-2, 3 - Diphe nyl-5- (4 - te r tb ut ylphe nylmethyle ne)- 4 -
thiazolidinone(1d):ꢀM.p.ꢀ249.0−250.5ꢀ°C;ꢀyieldꢀ81%.ꢀIR(KBr):ꢀ2966,ꢀ
2931,ꢀ1668,ꢀ1599,ꢀ1494ꢀcm–1.ꢀ1HꢀNMRꢀ(500ꢀMHz,ꢀCDCl3):ꢀδꢀ7.67ꢀ(s,ꢀ
1H),ꢀ 7.50ꢀ (d,ꢀ 2H,ꢀ J=ꢀ8.5ꢀHz),ꢀ 7.44ꢀ (d,ꢀ 2H,ꢀ J=ꢀ8.5ꢀHz),ꢀ 7.32−7.25ꢀ (m,ꢀ
9H),ꢀ7.18ꢀ(t,ꢀ1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ6.27ꢀ(s,ꢀ1H),ꢀ1.33ꢀ(m,ꢀ9H).ꢀAnal.ꢀcalcdꢀforꢀ
C26H25NOS:ꢀC,ꢀ78.16;ꢀH,ꢀ6.31;ꢀN,ꢀ3.51;ꢀfound:ꢀC,ꢀ78.24;ꢀH,ꢀ6.30;ꢀN,ꢀ
3.39%.
(Z)-2-Phenyl-3-(4-isopropylphenyl)-5-phenylmethylene-4-
thiazolidinone (1e):ꢀM.p.ꢀ194.4ꢀ°C;ꢀyieldꢀ78%.ꢀIR(KBr):ꢀ3030,ꢀ2962,ꢀ
2933,ꢀ 1666,ꢀ 1595,ꢀ 1514,ꢀ 1491ꢀcm–1.ꢀ 1Hꢀ NMRꢀ (500ꢀMHz,ꢀ CDCl3):ꢀ δꢀ
7.67ꢀ(s,ꢀ1H),ꢀ7.55ꢀ(d,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ7.41ꢀ(t,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ7.33−7.27ꢀ
(m,ꢀ6H),ꢀ7.15ꢀ(s,ꢀ4H),ꢀ6.23ꢀ(s,ꢀ1H),ꢀ2.87−2.79ꢀ(m,ꢀ1H),ꢀ1.18ꢀ(d,ꢀ6H,ꢀ
J=ꢀ7.0ꢀHz).ꢀ Anal.ꢀ calcdꢀ forꢀ C25H23NOS:ꢀ C,ꢀ 77.89;ꢀ H,ꢀ 6.01;ꢀ N,ꢀ 3.63;ꢀ
found:ꢀC,ꢀ77.78;ꢀH,ꢀ6.12;ꢀN,ꢀ3.67%.
(Z)-2-Phenyl-3-(4-isopropylphenyl)-5-(4-methylphenylmethylene)-
4-thiazolidinone (1f):ꢀ M.p.ꢀ 204.8−205.7ꢀ°C;ꢀ yieldꢀ 80%.ꢀ IR(KBr):ꢀ
3030,ꢀ2960,ꢀ2918,ꢀ1666,ꢀ1597,ꢀ1510ꢀcm–1.ꢀ1HꢀNMRꢀ(500ꢀMHz,ꢀCDCl3):ꢀ
δꢀ7.65ꢀ(s,ꢀ1H),ꢀ7.44ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.0ꢀHz),ꢀ7.33−7.26ꢀ(m,ꢀ5H),ꢀ7.22ꢀ(d,ꢀ2H,ꢀ
J=ꢀ8.0ꢀHz),ꢀ7.15ꢀ(s,ꢀ4H),ꢀ6.22ꢀ(s,ꢀ1H),ꢀ2.87−2.79ꢀ(m,ꢀ1H),ꢀ2.49ꢀ(s,ꢀ3H),ꢀ
1.18ꢀ(d,ꢀ6H,ꢀJ=ꢀ7.0ꢀHz).ꢀAnal.ꢀcalcdꢀforꢀC26H25NOS:ꢀC,ꢀ78.16;ꢀH,ꢀ6.31;ꢀN,ꢀ
3.51;ꢀfound:ꢀC,ꢀ78.22;ꢀH,ꢀ6.27;ꢀN,ꢀ3.45%.
(Z)-2-Phenyl-3-(4-isopropylphenyl)-5-(4-isopropylphenylmethylene)-
4-thiazolidinone (1g):ꢀM.p.ꢀ223.2−224.0ꢀ°C;ꢀyieldꢀ77%.ꢀIR(KBr):ꢀ2957,ꢀ
2924,ꢀ2866,ꢀ1668,ꢀ1597,ꢀ1510ꢀcm–1.ꢀ1HꢀNMRꢀ(500ꢀMHz,ꢀCDCl3):ꢀδꢀ7.66ꢀ
(s,ꢀ1H),ꢀ7.48ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.0ꢀHz),ꢀ7.32−7.26ꢀ(m,ꢀ7H),ꢀ7.15ꢀ(s,ꢀ4H),ꢀ6.22ꢀ(s,ꢀ
1H),ꢀ2.95−2.89ꢀ(m,ꢀ1H),ꢀ2.86−2.80ꢀ(m,ꢀ1H),ꢀ1.25ꢀ(d,ꢀ6H,ꢀJ=ꢀ7.0ꢀHz),ꢀ1.18ꢀ
(d,ꢀ6H,ꢀJ=ꢀ7.0ꢀHz).ꢀAnal.ꢀcalcdꢀforꢀC28H29NOS:ꢀC,ꢀ78.65;ꢀH,ꢀ6.84;ꢀN,ꢀ
3.28;ꢀfound:ꢀC,ꢀ78.67;ꢀH,ꢀ6.78;ꢀN,ꢀ3.23%.
(Z)-2-Phenyl-3-(4-isopropylphenyl)-5-(4-tertbutylphenyl-
methylene)-4-thiazolidinone (1h):ꢀ M.p.ꢀ 229.0−230.4ꢀ°C;ꢀ yieldꢀ 81%.ꢀ
IR(KBr):ꢀ3030,ꢀ2960,ꢀ2922,ꢀ1666,ꢀ1597,ꢀ1512ꢀcm–1.ꢀ1HꢀNMRꢀ(500ꢀMHz,ꢀ
CDCl3):ꢀδꢀ7.66ꢀ(s,ꢀ1H),ꢀ7.50ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.0ꢀHz),ꢀ7.32−7.24ꢀ(m,ꢀ7H),ꢀ7.15ꢀ
(s,ꢀ4H),ꢀ6.22ꢀ(s,ꢀ1H),ꢀ2.87−2.80ꢀ(m,ꢀ1H),ꢀ1.18ꢀ(d,ꢀ6H,ꢀJ=ꢀ7.0ꢀHz),ꢀ1.33ꢀ(s,ꢀ
9H).ꢀAnal.ꢀcalcdꢀforꢀC29H31NOS:ꢀC,ꢀ78.87;ꢀH,ꢀ7.08;ꢀN,ꢀ3.17;ꢀfound:ꢀC,ꢀ
78.92;ꢀH,ꢀ6.91;ꢀN,ꢀ3.15%.
(Z)-2-(4-Methylphenyl)-3-(4-chlorophenyl)-5-phenylmethylene-
4-thiazolidinone (1i):ꢀ M.p.ꢀ 191.2−191.8ꢀ°C;ꢀ yieldꢀ 75%.ꢀ IR(KBr):ꢀ
3030,ꢀ 2922,ꢀ 1664,ꢀ 1597,ꢀ 1493ꢀcm–1.ꢀ 1Hꢀ NMRꢀ (500ꢀMHz,ꢀ CDCl3):ꢀ δꢀ
7.67ꢀ(s,ꢀ1H),ꢀ7.54ꢀ(d,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ7.42ꢀ(t,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ7.31ꢀ(t,ꢀ1H,ꢀ
J=ꢀ7.0ꢀHz),ꢀ7.28−7.18ꢀ(m,ꢀ6H),ꢀ7.10ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.0ꢀHz),ꢀ6.21ꢀ(s,ꢀ1H),ꢀ2.30ꢀ
(s,ꢀ3H).ꢀAnal.ꢀcalcdꢀforꢀC23H18ClNOS:ꢀC,ꢀ70.49;ꢀH,ꢀ4.63;ꢀN,ꢀ3.57;ꢀfound:ꢀ
C,ꢀ70.42;ꢀH,ꢀ4.75;ꢀN,ꢀ3.69%.
Synthesisꢀꢀꢀꢀofꢀꢀꢀꢀ2′′,3′′,4′-triaryl-1′-methyldispiro[indole-3,2′-
pyrrolidine-3′,5′′-[1,3]thiazolane]-2(1H),4′′-dioneꢀ derivativesꢀ 4a–k;
general procedure
Aꢀ stirredꢀ mixtureꢀ ofꢀ 2,3-diaryl-5-arylmethylene-4-thiazolidinoneꢀ
(1.0ꢀmmol),ꢀ isatinꢀ (1.2ꢀmmol)ꢀ andꢀ sarcosineꢀ (1.2ꢀmmol)ꢀ inꢀ tolueneꢀ
(20ꢀmL)ꢀwasꢀheatedꢀunderꢀrefluxꢀconditionꢀforꢀ4ꢀh.ꢀAfterꢀcompletionꢀ
ofꢀ theꢀ reactionꢀ asꢀ indicatedꢀ byꢀ TLCꢀ analysis,ꢀ theꢀ mixtureꢀ wasꢀ
allowedꢀtoꢀcoolꢀtoꢀroomꢀtemperatureꢀandꢀtheꢀsolventꢀwasꢀevaporatedꢀ
underꢀreducedꢀpressure.ꢀTheꢀcrudeꢀproductꢀwasꢀsubjectedꢀtoꢀcolumnꢀ
chromatographyꢀ usingꢀ dichloromethaneꢀ:ꢀpetroleumꢀ etherꢀ (1ꢀ:ꢀ1)ꢀ asꢀ
eluentꢀtoꢀaffordꢀtheꢀpureꢀproductꢀ4a–k.
2 ′ ′ , 3 ′ ′ , 4 ′ -Tr i p h e n y l - 1′ - m e t h y l d i s p i r o [i n d o l e - 3 , 2 ′ -
pyrrolidine-3′,5′′-[1,3]thiazolane]-2(1H),4′′-dione (4a):ꢀIR(KBr):ꢀ3084,ꢀ
3061,ꢀ3026,ꢀ2940,ꢀ2887,ꢀ1720,ꢀ1682,ꢀ1620,ꢀ1493,ꢀ1472ꢀcm–1.ꢀ1HꢀNMRꢀ
(500ꢀMHz,ꢀDMSO):ꢀδꢀ10.69ꢀ(s,ꢀ1H),ꢀ7.56ꢀ(d,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ7.35−7.31ꢀ
(m,ꢀ3H),ꢀ7.24ꢀ(t,ꢀ1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ7.13ꢀ(t,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ7.06−7.03ꢀ(m,ꢀ
4H),ꢀ6.97ꢀ(t,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ6.92−6.91ꢀ(m,ꢀ2H),ꢀ6.74ꢀ(t,ꢀ1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ
6.59ꢀ(d,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ5.43ꢀ(s,ꢀ1H),ꢀ4.64ꢀ(t,ꢀ1H,ꢀJ=ꢀ9.0ꢀHz),ꢀ3.90ꢀ(t,ꢀ
1H,ꢀ J=ꢀ9.0ꢀHz),ꢀ3.49ꢀ(t,ꢀ1H,ꢀJ=ꢀ9.0ꢀHz),ꢀ2.09ꢀ(s,ꢀ3H).ꢀAnal.ꢀcalcdꢀforꢀ
C32H27N3O2S:ꢀC,ꢀ74.25;ꢀH,ꢀ5.26;ꢀN,ꢀ8.12;ꢀfound:ꢀC,ꢀ74.32;ꢀH,ꢀ5.33;ꢀN,ꢀ
8.28%.
4′-(4-Methylphenyl)-2′′,3′′-diphenyl-1′-methyldispiro[indole-3,2′-
pyrrolidine-3′,5′′-[1,3]thiazolane]-2(1H),4′′-dione (4b):ꢀ IR(KBr):ꢀ
3250,ꢀ3058,ꢀ3030,ꢀ2870,ꢀ1713,ꢀ1666,ꢀ1618,ꢀ1593,ꢀ1492,ꢀ1470,ꢀ1396ꢀcm–1.ꢀ
1HꢀNMRꢀ(500ꢀMHz,ꢀDMSO):ꢀδꢀ10.45ꢀ(s,ꢀ1H),ꢀ7.67ꢀ(d,ꢀ1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ
7.48ꢀ(t,ꢀ1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ7.30−7.24ꢀ(m,ꢀ5H),ꢀ7.20−7.10ꢀ(m,ꢀ5H),ꢀ6.99ꢀ(t,ꢀ
1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ6.89−6.83ꢀ(m,ꢀ3H),ꢀ6.27ꢀ(d,ꢀ2H,ꢀJ=ꢀ7.0ꢀHz),ꢀ5.96ꢀ(s,ꢀ1H),ꢀ
4.42ꢀ(t,ꢀ1H,ꢀJ=ꢀ9.0ꢀHz),ꢀ3.83ꢀ(t,ꢀ1H,ꢀJ=ꢀ9.0ꢀHz),ꢀ3.39ꢀ(t,ꢀ1H,ꢀJ=ꢀ8.0ꢀHz),ꢀ
2.32ꢀ(s,ꢀ3H),ꢀ2.11ꢀ(s,ꢀ3H).ꢀAnal.ꢀcalcdꢀforꢀC33H29N3O2S:ꢀC,ꢀ74.55;ꢀH,ꢀ5.50;ꢀ
N,ꢀ7.90;ꢀfound:ꢀC,ꢀ74.43;ꢀH,ꢀ5.37;ꢀN,ꢀ8.01%.
4′-(4-Isopropylphenyl)-2′′,3′′-diphenyl-1′-methyldispiro[indole-3,2′-
pyrrolidine-3′,5′′-[1,3]thiazolane]-2(1H),4′′-dione (4c):ꢀIR(KBr):ꢀ2959,ꢀ
2870,ꢀ1724,ꢀ1680,ꢀ1618,ꢀ1492,ꢀ1470ꢀcm–1.ꢀ1HꢀNMRꢀ(500ꢀMHz,ꢀDMSO):ꢀ
δꢀ10.68ꢀ(s,ꢀ1H),ꢀ7.46ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.0ꢀHz),ꢀ7.32ꢀ(t,ꢀ1H,ꢀJ=ꢀ8.0ꢀHz),ꢀ7.21ꢀ(d,ꢀ
2H,ꢀJ=ꢀ8.0ꢀHz),ꢀ7.13ꢀ(t,ꢀ2H,ꢀJ=ꢀ8.0ꢀHz),ꢀ7.05−7.02ꢀ(m,ꢀ4H),ꢀ6.96ꢀ(t,ꢀ2H,ꢀ
J=ꢀ7.0ꢀHz),ꢀ 6.92−6.90ꢀ (m,ꢀ 2H),ꢀ 6.73ꢀ (t,ꢀ 1H,ꢀ J=ꢀ7.5ꢀHz),ꢀ 6.58ꢀ (d,ꢀ 2H,ꢀ
J=ꢀ8.0ꢀHz),ꢀ5.44ꢀ(s,ꢀ1H),ꢀ4.61ꢀ(t,ꢀ1H,ꢀJ=ꢀ7.0ꢀHz),ꢀ3.86ꢀ(t,ꢀ1H,ꢀJ=ꢀ9.5ꢀHz),ꢀ
3.45ꢀ(t,ꢀ1H,ꢀJ=ꢀ8.5ꢀHz),ꢀ2.89−2.81ꢀ(m,ꢀ1H),ꢀ2.08ꢀ(s,ꢀ3H),ꢀ1.17ꢀ(d,ꢀ6H,ꢀ
J=ꢀ7.0ꢀHz).ꢀ Anal.ꢀ calcdꢀ forꢀ C35H33N3O2S:ꢀ C,ꢀ 75.10;ꢀ H,ꢀ 5.94;ꢀ N,ꢀ 7.51;ꢀ
found:ꢀC,ꢀ74.98;ꢀH,ꢀ5.87;ꢀN,ꢀ7.68%.
2′′,3′′-Diphenyl-4′-(4-tertbutylphenyl)-1′-methyldispiro[indole-
3,2′-pyrrolidine-3′,5′′-[1,3]thiazolane]-2(1H),4′′-dione (4d):ꢀ IR(KBr):ꢀ
2949,ꢀ 2897,ꢀ 1724,ꢀ 1678,ꢀ 1620,ꢀ 1471,ꢀ 1458ꢀcm–1.ꢀ 1Hꢀ NMRꢀ (500ꢀMHz,ꢀ
DMSO):ꢀδꢀ10.68ꢀ(s,ꢀ1H),ꢀ7.48ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.5ꢀHz),ꢀ7.36ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.5ꢀHz),ꢀ
7.32ꢀ(t,ꢀ1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ7.13ꢀ(t,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ7.05−7.01ꢀ(m,ꢀ4H),ꢀ6.97ꢀ
(d,ꢀ 2H,ꢀ J=ꢀ8.5ꢀHz),ꢀ 6.92−6.90ꢀ (m,ꢀ 2H),ꢀ 6.73ꢀ (t,ꢀ 1H,ꢀ J=ꢀ8.0ꢀHz),ꢀ 6.58ꢀ
(d,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ5.44ꢀ(s,ꢀ1H),ꢀ4.61ꢀ(t,ꢀ1H,ꢀJ=ꢀ8.5ꢀHz),ꢀ3.87ꢀ(t,ꢀ1H,ꢀ
J=ꢀ9.0ꢀHz),ꢀ3.45ꢀ(t,ꢀ1H,ꢀJ=ꢀ9.0ꢀHz),ꢀ2.08ꢀ(s,ꢀ3H),ꢀ1.26ꢀ(s,ꢀ9H).ꢀAnal.ꢀcalcdꢀ
forꢀC36H35N3O2S:ꢀC,ꢀ75.36;ꢀH,ꢀ6.15;ꢀN,ꢀ7.32;ꢀfound:ꢀC,ꢀ75.38;ꢀH,ꢀ6.22;ꢀN,ꢀ
7.24%.
3′′-(4-Isopropylphenyl)-2′′,4′-diphenyl-1′-methyldispiro[indole-
3,2′-pyrrolidine-3′,5′′-[1,3]thiazolane]-2(1H),4′′-dione (4e):ꢀ IR(KBr):ꢀ
3258,ꢀ3057,ꢀ2953,ꢀ2881,ꢀ1724,ꢀ1672,ꢀ1612,ꢀ1510,ꢀ1467ꢀcm–1.ꢀ1HꢀNMRꢀ

286ꢀꢀꢀJOURNALꢀOFꢀCHEMICALꢀRESEARCHꢀ2014
(500ꢀMHz,ꢀDMSO):ꢀδꢀ10.67ꢀ(s,ꢀ1H),ꢀ7.55ꢀ(d,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ7.36−7.32ꢀ
(m,ꢀ3H),ꢀ7.23ꢀ(t,ꢀ1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ7.05−6.96ꢀ(m,ꢀ7H),ꢀ6.91−6.89ꢀ(m,ꢀ2H),ꢀ
6.72ꢀ(t,ꢀ1H,ꢀJ=ꢀ8.0ꢀHz),ꢀ6.49ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.5ꢀHz),ꢀ5.39ꢀ(s,ꢀ1H),ꢀ4.63ꢀ(t,ꢀ1H,ꢀ
J=ꢀ8.0ꢀHz),ꢀ3.90ꢀ(t,ꢀ1H,ꢀJ=ꢀ9.0ꢀHz),ꢀ3.49ꢀ(t,ꢀ1H,ꢀJ=ꢀ8.5ꢀHz),ꢀ2.78−2.69ꢀ(m,ꢀ
1H),ꢀ2.09ꢀ(s,ꢀ3H),ꢀ1.08ꢀ(d,ꢀ6H,ꢀJ=ꢀ7.0ꢀHz).ꢀAnal.ꢀcalcdꢀforꢀC35H33N3O2S:ꢀ
C,ꢀ75.10;ꢀH,ꢀ5.94;ꢀN,ꢀ7.51;ꢀfound:ꢀC,ꢀ75.05;ꢀH,ꢀ6.10;ꢀN,ꢀ7.43%.
3′′-(4-Isopropylphenyl)-4′-(4-methylphenyl)-2′′-phenyl-1′-
methyldispiro[indole-3,2′-pyrrolidine-3′,5′′-[1,3]thiazolane]-
2(1H),4′′-dione (4f):ꢀ IR(KBr):ꢀ 2961,ꢀ 2876,ꢀ 1720,ꢀ 1678,ꢀ 1600,ꢀ 1510,ꢀ
1475ꢀcm–1.ꢀ1HꢀNMRꢀ(500ꢀMHz,ꢀDMSO):ꢀδꢀ10.66ꢀ(s,ꢀ1H),ꢀ7.43ꢀ(d,ꢀ2H,ꢀ
J=ꢀ8.0ꢀHz),ꢀ7.33ꢀ(t,ꢀ1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ7.14ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.0ꢀHz),ꢀ7.05−7.04ꢀ
(m,ꢀ3H),ꢀ7.01−6.96ꢀ(m,ꢀ4H),ꢀ6.92−6.90ꢀ(m,ꢀ2H),ꢀ6.75ꢀ(t,ꢀ1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ
6.49ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.5ꢀHz),ꢀ5.38ꢀ(s,ꢀ1H),ꢀ4.58ꢀ(t,ꢀ1H,ꢀJ=ꢀ8.0ꢀHz),ꢀ3.86ꢀ(t,ꢀ1H,ꢀ
J=ꢀ9.0ꢀHz),ꢀ3.45ꢀ(t,ꢀ1H,ꢀJ=ꢀ8.5ꢀHz),ꢀ2.77−2.69ꢀ(m,ꢀ1H),ꢀ2.25ꢀ(s,ꢀ3H),ꢀ2.08ꢀ
(s,ꢀ3H),ꢀ1.08ꢀ(d,ꢀ6H,ꢀJ=ꢀ7.0ꢀHz).ꢀAnal.ꢀcalcdꢀforꢀC36H35N3O2S:ꢀC,ꢀ75.36;ꢀ
H,ꢀ6.15;ꢀN,ꢀ7.32;ꢀfound:ꢀC,ꢀ75.27;ꢀH,ꢀ6.19;ꢀN,ꢀ7.40%.
(m,ꢀ2H),ꢀ5.37ꢀ(s,ꢀ1H),ꢀ4.57ꢀ(t,ꢀ1H,ꢀJ=ꢀ9.0ꢀHz),ꢀ3.86ꢀ(t,ꢀ1H,ꢀJ=ꢀ9.0ꢀHz),ꢀ3.45ꢀ
(t,ꢀ1H,ꢀJ=ꢀ8.5ꢀHz),ꢀ2.26ꢀ(s,ꢀ3H),ꢀ2.08ꢀ(s,ꢀ3H),ꢀ2.07ꢀ(s,ꢀ3H).ꢀAnal.ꢀcalcdꢀforꢀ
C34H30ClN3O2S:ꢀC,ꢀ70.39;ꢀH,ꢀ5.21;ꢀN,ꢀ7.24;ꢀfound:ꢀC,ꢀ70.42;ꢀH,ꢀ5.11;ꢀN,ꢀ
7.40%.
3′′-(4-Chlorophenyl)-4′-(4-isopropylphenyl)-2′′-(4-methylphenyl)-
1′-methyldispiro[indole-3,2′-pyrrolidine-3′,5′′-[1,3]thiazolane]-
2(1H),4′′-dione (4k):ꢀ IR(KBr):ꢀ 2942,ꢀ 2872,ꢀ 1724,ꢀ 1680,ꢀ 1618,ꢀ 1493,ꢀ
1472ꢀcm–1.ꢀ1HꢀNMRꢀ(500ꢀMHz,ꢀDMSO):ꢀδꢀ10.69ꢀ(s,ꢀ1H),ꢀ7.46ꢀ(d,ꢀ2H,ꢀ
J=ꢀ8.5ꢀHz),ꢀ 7.31ꢀ (t,ꢀ 1H,ꢀ J=ꢀ8.0ꢀHz),ꢀ 7.22−7.20ꢀ (m,ꢀ 4H),ꢀ 6.98ꢀ (d,ꢀ 1H,ꢀ
J=ꢀ7.5ꢀHz),ꢀ6.91ꢀ(d,ꢀ1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ6.85ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.0ꢀHz),ꢀ6.80ꢀ(d,ꢀ2H,ꢀ
J=ꢀ8.0ꢀHz),ꢀ6.73ꢀ(t,ꢀ 1H,ꢀ J=ꢀ7.5ꢀHz),ꢀ 6.64−6.62ꢀ(m,ꢀ2H),ꢀ 5.39ꢀ (s,ꢀ1H),ꢀ
4.60ꢀ(t,ꢀ1H,ꢀJ=ꢀ8.5ꢀHz),ꢀ3.87ꢀ(t,ꢀ1H,ꢀJ=ꢀ9.0ꢀHz),ꢀ3.48ꢀ(t,ꢀ1H,ꢀJ=ꢀ8.5ꢀHz),ꢀ
2.89−2.80ꢀ(m,ꢀ1H),ꢀ2.51−2.50ꢀ(m,ꢀ6H),ꢀ1.17ꢀ(d,ꢀ6H,ꢀJ=ꢀ7.0ꢀHz).ꢀAnal.ꢀ
calcdꢀforꢀC36H34ClN3O2S:ꢀC,ꢀ71.09;ꢀH,ꢀ5.63;ꢀN,ꢀ6.91;ꢀfound:ꢀC,ꢀ70.97;ꢀH,ꢀ
5.76;ꢀN,ꢀ7.01%.
3′′,4′-Di(4-isopropylphenyl)-2′′-phenyl-1′-methyldispiro[indole-
3,2′-pyrrolidine-3′,5′′-[1,3]thiazolane]-2(1H),4′′-dione (4g):ꢀ IR(KBr):ꢀ
2959,ꢀ2872,ꢀ1724,ꢀ1674,ꢀ1602,ꢀ1514,ꢀ1470ꢀcm–1.ꢀ1HꢀNMRꢀ(500ꢀMHz,ꢀ
DMSO):ꢀδꢀ10.66ꢀ(s,ꢀ1H),ꢀ7.46ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.0ꢀHz),ꢀ7.33ꢀ(t,ꢀ1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ
7.21ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.5ꢀHz),ꢀ7.05−6.96ꢀ(m,ꢀ7H),ꢀ6.91−6.89ꢀ(m,ꢀ2H),ꢀ6.76ꢀ
(t,ꢀ1H,ꢀJ=ꢀ8.0ꢀHz),ꢀ6.49ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.5ꢀHz),ꢀ5.40ꢀ(s,ꢀ1H),ꢀ4.59ꢀ(t,ꢀ1H,ꢀ
J=ꢀ8.5ꢀHz),ꢀ3.86ꢀ(t,ꢀ1H,ꢀJ=ꢀ9.0ꢀHz),ꢀ3.45ꢀ(t,ꢀ1H,ꢀJ=ꢀ8.5ꢀHz),ꢀ2.88−2.82ꢀ(m,ꢀ
1H),ꢀ2.76−2.71ꢀ(m,ꢀ1H),ꢀ2.08ꢀ(s,ꢀ3H),ꢀ1.17ꢀ(d,ꢀ6H,ꢀJ=ꢀ7.0ꢀHz),ꢀ1.08ꢀ(d,ꢀ
6H,ꢀJ=ꢀ7.0ꢀHz).ꢀAnal.ꢀcalcdꢀforꢀC38H39N3O2S:ꢀC,ꢀ75.84;ꢀH,ꢀ6.53;ꢀN,ꢀ6.98;ꢀ
found:ꢀC,ꢀ75.77;ꢀH,ꢀ6.68;ꢀN,ꢀ7.02%.
Thisꢀ workꢀ wasꢀ partiallyꢀ supportedꢀ byꢀ theꢀ Naturalꢀ Scienceꢀ
Foundationꢀ ofꢀ Hebeiꢀ Provinceꢀ (no.ꢀ B2012208051),ꢀ Hebeiꢀ
Provinceꢀ Scienceꢀ andꢀ Technologyꢀ Supportꢀ Planꢀ Projectꢀ (no.ꢀ
12211405)ꢀandꢀtheꢀresearchꢀfoundationꢀofꢀtheꢀHebeiꢀUniversityꢀ
ofꢀScienceꢀandꢀTechnology.
Receivedꢀ29ꢀDecemberꢀ2013;ꢀacceptedꢀ3ꢀMarchꢀ2014
Paperꢀ1302369ꢀdoi:ꢀ10.3184/174751914X13965156954070
Publishedꢀonline:ꢀ6ꢀMayꢀ2014
4′-(4-Isopropylphenyl)-2′′-phenyl-3′′-(4-tertbutylphenyl)-1′-
methyldispiro[indole-3,2′-pyrrolidine-3′,5′′-[1,3]thiazolane]-
2(1H),4′′-dione (4h):ꢀIR(KBr):ꢀ2963,ꢀ2872,ꢀ1726,ꢀ1676,ꢀ1514,ꢀ1470ꢀcm–1.ꢀ
1HꢀNMRꢀ(500ꢀMHz,ꢀDMSO):ꢀδꢀ10.67ꢀ(s,ꢀ1H),ꢀ7.46ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.0ꢀHz),ꢀ
7.37−7.33ꢀ (m,ꢀ 3H),ꢀ 7.04−6.96ꢀ (m,ꢀ 7H),ꢀ 6.90ꢀ (s,ꢀ 2H),ꢀ 6.76ꢀ (t,ꢀ 1H,ꢀ
J=ꢀ7.5ꢀHz),ꢀ6.49ꢀ(d,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ5.40ꢀ(s,ꢀ1H),ꢀ4.59ꢀ(t,ꢀ1H,ꢀJ=ꢀ8.5ꢀHz),ꢀ
3.85ꢀ(t,ꢀ1H,ꢀJ=ꢀ8.5ꢀHz),ꢀ3.43ꢀ(t,ꢀ1H,ꢀJ=ꢀ8.0ꢀHz),ꢀ2.74ꢀ(t,ꢀ1H,ꢀJ=ꢀ6.5ꢀHz),ꢀ
2.07ꢀ (s,ꢀ 3H),ꢀ 1.25ꢀ (s,ꢀ 9H),ꢀ 1.08ꢀ (d,ꢀ 6H,ꢀ J=ꢀ6.5ꢀHz).ꢀ Anal.ꢀ calcdꢀ forꢀ
C39H41N3O2S:ꢀC,ꢀ76.06;ꢀH,ꢀ6.71;ꢀN,ꢀ6.82;ꢀfound:ꢀC,ꢀ76.17;ꢀH,ꢀ6.59;ꢀN,ꢀ
6.86%.
3′′-(4-Chlorophenyl)-2′′-(4-methylphenyl)-4′-phenyl-1′-
methyldispiro[indole-3,2′-pyrrolidine-3′,5′′-[1,3]thiazolane]-
2(1H),4′′-dione (4i):ꢀIR(KBr):ꢀ2949,ꢀ2866,ꢀ1693,ꢀ1618,ꢀ1493,ꢀ1469ꢀcm–1.ꢀ
1HꢀNMRꢀ(500ꢀMHz,ꢀDMSO):ꢀδꢀ10.68ꢀ(s,ꢀ1H),ꢀ7.54ꢀ(d,ꢀ2H,ꢀJ=ꢀ7.5ꢀHz),ꢀ
7.35−7.30ꢀ(m,ꢀ3H),ꢀ7.25−7.20ꢀ(m,ꢀ3H),ꢀ6.97ꢀ(d,ꢀ1H,ꢀJ=ꢀ8.0ꢀHz),ꢀ6.91ꢀ(d,ꢀ
1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ6.87−6.79ꢀ(m,ꢀ4H),ꢀ6.73ꢀ(t,ꢀ1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ6.63ꢀ(d,ꢀ2H,ꢀ
J=ꢀ9.0ꢀHz),ꢀ5.38ꢀ(s,ꢀ1H),ꢀ4.62ꢀ(t,ꢀ1H,ꢀJ=ꢀ9.0ꢀHz),ꢀ3.89ꢀ(t,ꢀ1H,ꢀJ=ꢀ9.0ꢀHz),ꢀ
3.48ꢀ (t,ꢀ 1H,ꢀ J=ꢀ8.5ꢀHz),ꢀ 2.07ꢀ (d,ꢀ 6H,ꢀ J=ꢀ4.5ꢀHz).ꢀ Anal.ꢀ calcdꢀ forꢀ
C33H28ClN3O2S:ꢀC,ꢀ70.01;ꢀH,ꢀ4.99;ꢀN,ꢀ7.42;ꢀfound:ꢀC,ꢀ69.87;ꢀH,ꢀ5.09;ꢀN,ꢀ
7.39%.
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3′′-(4-Chlorophenyl)-2′′,4-di(4-methylphenyl)-1′-methyl-
dispiro[indole-3,2′-pyrrolidine-3,5′′-[1,3]thiazolane]-2(1H),4′′-dione
(4j):ꢀIR(KBr):ꢀ3318,ꢀ2868,ꢀ2795,ꢀ1717,ꢀ1694,ꢀ1618,ꢀ1493,ꢀ1468ꢀcm–1.ꢀ1Hꢀ
NMRꢀ(500ꢀMHz,ꢀDMSO):ꢀδꢀ10.66ꢀ(s,ꢀ1H),ꢀ7.42ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.0ꢀHz),ꢀ7.30ꢀ
(t,ꢀ1H,ꢀJ=ꢀ8.0ꢀHz),ꢀ7.22−7.20ꢀ(m,ꢀ2H),ꢀ7.13ꢀ(d,ꢀ2H,ꢀJ=ꢀ8.0ꢀHz),ꢀ6.96ꢀ(d,ꢀ
1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ6.89−6.79ꢀ(m,ꢀ5H),ꢀ6.72ꢀ(t,ꢀ1H,ꢀJ=ꢀ7.5ꢀHz),ꢀ6.63−6.61ꢀ
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