Direct dihalo-alkoxylation of nitroalkenes leading to β,β-dihalo-β-nitroethyl alkyl ethers

Article abstract of DOI:10.1039/c8ob00408k

A highly efficient one-pot synthesis of β,β-dihalo-β-nitroethyl alkyl ethers is achieved by the treatment of nitroalkenes with alcohols and N-halosuccinimides in the presence of sodium hydride. The notable advantages of this protocol are that it involves simple experimental manipulations and tolerates a wide range of functional groups. Further transformations of the obtained ethers, such as allylation and conversion to β,β-dihalogenated vinyl ethers, are also investigated.

Full text of DOI:10.1039/c8ob00408k

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January 2016 Pages 1–372
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COMMUNICATION
Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
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O rP gl ea na si ce &ꢀ d Bo i ꢀon mo to ꢀ al e dc juu l sa tr ꢀ mC haer mg i ins ts rꢀ y
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DOI: 10.1039/C8OB00408K
JournalꢀNameꢀ
ꢀ
ARTICLEꢀ
Directꢀdihalo-alkoxylationꢀofꢀnitroalkenesꢀleadingꢀtoꢀ
nitroethylꢀalkylꢀethersꢀꢀ
, -dihalo- -
b b b
a
a,b
ꢀ a,bꢀ
FeiyueꢀHao, ꢀSoichiꢀYokoyama ꢀandꢀNagatoshiꢀNishiwaki *
Receivedꢀ00thꢀJanuaryꢀ20xx,ꢀ
Acceptedꢀ00thꢀJanuaryꢀ20xxꢀ
Aꢀhighlyꢀefficientꢀone-potꢀsynthesisꢀofꢀb,b-dihalo-β-nitroethylꢀalkylꢀethersꢀisꢀachievedꢀbyꢀtreatmentꢀofꢀnitroalkenesꢀwithꢀ
alcoholsꢀandꢀN-halosuccinimidesꢀinꢀtheꢀpresenceꢀofꢀsodiumꢀhydride.ꢀTheꢀnotableꢀadvantagesꢀofꢀthisꢀprotocolꢀareꢀthatꢀitꢀ
involvesꢀsimpleꢀexperimentalꢀmanipulationsꢀandꢀtoleratesꢀaꢀwideꢀrangeꢀofꢀfunctionalꢀgroups.ꢀFurtherꢀtransformationsꢀofꢀtheꢀ
obtainedꢀethers,ꢀsuchꢀasꢀallylationꢀandꢀconversionꢀtoꢀb,b-dihalogenatedꢀvinylꢀethers,ꢀareꢀalsoꢀinvestigated.
DOI:ꢀ10.1039/x0xx00000xꢀ
www.rsc.org/ꢀ
facilitateꢀtheꢀdirectꢀdihalo-alkoxylationꢀunderꢀmildꢀconditions,ꢀ
leadingꢀtoꢀdiverseꢀβ,β-dihalo-β-nitroethylꢀalkylꢀethers,ꢀwhichꢀareꢀ
Introductionꢀ
1
a,eꢀ
oftenꢀfoundꢀasꢀmotifsꢀinꢀbiologicallyꢀactiveꢀcompounds.
Theꢀhighlyꢀelectron-deficientꢀdihalo(nitro)methylꢀunitꢀisꢀoneꢀofꢀ
theꢀmostꢀimportantꢀstructuralꢀmotifsꢀfoundꢀinꢀbiologicallyꢀactiveꢀ
1
compoundsꢀandꢀagrochemicals. ꢀTheꢀdihalo(nitro)methylꢀgroupꢀ
Resultsꢀandꢀdiscussionꢀ
alsoꢀservesꢀasꢀaꢀprecursorꢀforꢀversatileꢀfunctionalꢀgroupsꢀsuchꢀasꢀ
2
,3
Toꢀ evaluateꢀ theꢀ potentialꢀ forꢀ vicinalꢀ functionalization,ꢀ β-
nitrostyreneꢀ1aꢀwasꢀchosenꢀasꢀaꢀmodelꢀsubstrate.ꢀꢀTheꢀreactionꢀ
ofꢀ1aꢀwithꢀMeOHꢀ2aꢀandꢀNCSꢀinꢀtheꢀpresenceꢀofꢀt-BuOKꢀinꢀTHFꢀꢀ
dihalomethylꢀ andꢀ amideꢀ groups. ꢀ Therefore,ꢀ variousꢀ
approachesꢀ towardꢀ functionalizedꢀ compoundsꢀ containingꢀ aꢀ
dihalo(nitro)methylꢀgroupꢀhaveꢀbeenꢀdeveloped,ꢀsuchꢀasꢀα,α-
4
dihalogenationꢀ ofꢀ nitroalkanes ꢀ andꢀ nitrationꢀ ofꢀ
Tableꢀ1ꢀOptimizationꢀofꢀreactionꢀconditionsꢀ
1
b,5
trihalonitroalkenes. ꢀ Asꢀ anꢀ alternative,ꢀ dihalogenationꢀ ofꢀ
nitroalkenesꢀ accompaniedꢀ byꢀ vicinalꢀ functionalizationꢀ
representsꢀanꢀefficientꢀsingle-stepꢀapproachꢀtoꢀfunctionalizedꢀ
compoundsꢀpossessingꢀaꢀdihalo(nitro)methylꢀmoiety.ꢀUpꢀtoꢀnow,ꢀ
directꢀdihalo-amidationꢀofꢀnitroalkenesꢀhasꢀbeenꢀsubstantiallyꢀ
established,ꢀusingꢀanꢀarrayꢀofꢀnitrogen/halogenꢀsourcesꢀsuchꢀasꢀ
NO
2
MeOH 2a (5.0 equiv.)
NCS (2.1 equiv.)
Base (1.2 equiv.)
MeO
NO
Cl
Cl
2
Solv., rt, 5 h
6
7
succinimide/N-bromosuccinimideꢀ(NBS), ꢀandꢀbenzamide/NBS. ꢀ
8
Directꢀdihalo-amidationꢀusingꢀonlyꢀN-bromoacetamide ꢀorꢀN,N-
1a
3a
a
ꢀaꢀ
Entryꢀ
1ꢀ
Solv.ꢀ
THFꢀ
Baseꢀ
Yield ꢀ(%)ꢀ
Recov. (%)ꢀ
dichloro-p-toluenesulfonamideꢀ asꢀ theꢀ amido-halogenatingꢀ
9
agent ꢀ affordsꢀ N-β,β-dihalo-β-nitroethylamides,ꢀ whichꢀ areꢀ
t-BuOKꢀ
t-BuOKꢀ
t-BuOKꢀ
t-BuOKꢀ
t-BuOKꢀ
t-BuOKꢀ
t-BuOKꢀ
t-BuOKꢀ
t-BuOKꢀ
t-BuOKꢀ
21ꢀ
0ꢀ
0ꢀ
2ꢀ
MeCNꢀ
DMFꢀ
20ꢀ
1
0
usefulꢀprecursorsꢀforꢀfunctionalizedꢀ1,2-diamines. ꢀWhileꢀdirectꢀ
dihalo-amidationꢀofꢀnitroalkenesꢀhasꢀbeenꢀestablished,ꢀthereꢀisꢀ
onlyꢀoneꢀexampleꢀofꢀtheꢀdirectꢀhalo-alkoxylationꢀofꢀ1-nitro-1-
buteneꢀusingꢀsodiumꢀmethoxideꢀandꢀtheꢀtoxicꢀbromine,ꢀandꢀtheꢀ
3ꢀ
6ꢀ
0ꢀ
4
5
6
ꢀ
ꢀ
ꢀ
MeOHꢀ
24ꢀ
0ꢀ
Et
tolueneꢀ
ClCH CH Clꢀ
cyclohexaneꢀ
CHCl
2
Oꢀ
43ꢀ
10ꢀ
10ꢀ
15ꢀ
4ꢀ
35ꢀ
1
e
7ꢀ
2
2
29ꢀ
substrateꢀscopeꢀhasꢀnotꢀbeenꢀinvestigatedꢀfurther. ꢀMeanwhile,ꢀ
weꢀhaveꢀdisclosedꢀaꢀdirectꢀmethoxy-chlorinationꢀofꢀ1-methyl-3-
nitro-2-quinolonesꢀ usingꢀ sodiumꢀ methoxideꢀ andꢀ N-
8
9
ꢀ
ꢀ
11ꢀ
3
ꢀ
25ꢀ
28ꢀ
0ꢀ
1
1
1
0ꢀ
1ꢀ
2ꢀ
CH
CH
CH
2
2
2
Cl
2
ꢀ
ꢀ
ꢀ
51ꢀ
1
1
chlorosuccinimideꢀ (NCS). ꢀ Onꢀ theꢀ basisꢀ ofꢀ theseꢀ results,ꢀ weꢀ
envisageꢀ thatꢀ reactionsꢀ ofꢀ nitroalkenesꢀ withꢀ sodiumꢀ alkoxideꢀ
Cl
Cl
2
2
Et
3
Nꢀ
0ꢀ
100ꢀ
-ꢀ
b
DBUꢀ
c.m. ꢀ
1
2
generatedꢀ inꢀ situ ꢀ andꢀ readilyꢀ treatableꢀ N-halosuccinimideꢀ
13ꢀ
CH Cl ꢀ
2
2
2
2
2
2
2
2
2
2
NaOHꢀ
traceꢀ
traceꢀ
21ꢀ
0ꢀ
1
1
1
4ꢀ
5ꢀ
CH
CH
CH
CH
Cl
Cl
Cl
Cl
ꢀ
ꢀ
ꢀ
ꢀ
Cs
2
CO
3
ꢀ
0ꢀ
BuLiꢀ
NaHꢀ
NaHꢀ
0ꢀ
6ꢀ
c
97ꢀꢀ
0ꢀ
d
1
7 ꢀ
95ꢀ(90 )ꢀ
0ꢀ
a
1
Yieldꢀandꢀrecoveryꢀwereꢀdeterminedꢀbyꢀ HꢀNMRꢀofꢀtheꢀreactionꢀmixtureꢀusingꢀ
ꢀ
b
c
C
2 2 4
H Cl ꢀasꢀinternalꢀstandard. Complexꢀmixture.ꢀ Theꢀreactionꢀinvolvedꢀ2.0ꢀequiv.ꢀ
d
ofꢀMeOH.ꢀ Isolatedꢀyield.ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ1ꢀꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

O rP gl ea na si ce &ꢀ d Bo i ꢀon mo to ꢀ al e dc juu l sa tr ꢀ mC haer mg i ins ts rꢀ y
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ARTICLEꢀ
JournalꢀNameꢀ
successfullyꢀaffordedꢀ
1
b
,
b
-dichloro-β-nitroethylꢀmethylꢀetherꢀ3a
ꢀ
inꢀ 21%ꢀ yield. ꢀ Aproticꢀ solventsꢀ wereꢀ moreꢀ suitableꢀ forꢀ thisꢀ suchꢀasꢀethanol,ꢀpropanol,ꢀandꢀbenzylꢀalcohol,ꢀwhichꢀaffordedꢀ
Next,ꢀtheꢀscopeꢀofꢀthisꢀprotocolꢀwasꢀexpandedꢀtoꢀoVtiheweArꢀraticlcleoOhnolinlesꢀ
DOI: 10.1039/C8OB00408K
3
reaction,ꢀandꢀtheꢀyieldꢀincreasedꢀtoꢀ51%ꢀwhenꢀtheꢀreactionꢀwasꢀ theꢀcorrespondingꢀproductsꢀ3p
conductedꢀ inꢀ CH Cl ꢀ (entriesꢀ 1–10).ꢀ Inꢀ additionꢀ toꢀ t-BuOK,ꢀ 2–4).ꢀ However,ꢀ alcoholsꢀ suchꢀ asꢀ 2-phenylethanolꢀ 2sꢀ andꢀ 3-
severalꢀ otherꢀ organicꢀ andꢀ inorganicꢀ basesꢀ wereꢀ screenedꢀ methylbutanolꢀ 2tꢀ wereꢀ notꢀ sufficientlyꢀ convertedꢀ toꢀ theꢀ
entriesꢀ 11–16).ꢀ Althoughꢀ mostꢀ ofꢀ theseꢀ basesꢀ wereꢀ notꢀ alkoxides,ꢀasꢀreleaseꢀofꢀhydrogenꢀgasꢀwasꢀnotꢀobserved.ꢀThisꢀ
–rꢀinꢀgoodꢀyieldsꢀ(Tableꢀ3,ꢀentriesꢀ
2
2
(
effective,ꢀtheꢀyieldꢀincreasedꢀtoꢀ97%ꢀwhenꢀusingꢀsodiumꢀhydride,ꢀ issueꢀ wasꢀ overcomeꢀ byꢀ conductingꢀ theꢀ reactionꢀ atꢀ aꢀ higherꢀ
whichꢀ facilitatedꢀ aꢀ lowerꢀ loadingꢀ ofꢀ MeOHꢀ withoutꢀ anyꢀ temperatureꢀtoꢀfurnishꢀ3sꢀandꢀ3tꢀinꢀhigherꢀyields,ꢀrespectivelyꢀ
influenceꢀ onꢀ theꢀ yieldꢀ (entriesꢀ 16–17).ꢀ Overall,ꢀ theꢀ reactionꢀ (entriesꢀ5ꢀandꢀ6).ꢀWhileꢀtheꢀbulkyꢀisopropanolꢀ2uꢀgaveꢀ3uꢀinꢀ42%ꢀ
conditionsꢀusedꢀinꢀentryꢀ16ꢀwereꢀdeterminedꢀtoꢀbeꢀoptimal.ꢀ
Withꢀtheꢀoptimizedꢀreactionꢀconditionsꢀinꢀhand,ꢀweꢀscreenedꢀaꢀ mixtureꢀ(entriesꢀ7ꢀandꢀ8).ꢀWhenꢀalcoholsꢀ2w
yield,ꢀ theꢀ bulkierꢀ tert-butanolꢀ 2vꢀ furnishedꢀ aꢀ highlyꢀ complexꢀ
ꢀpossessingꢀ2,2,2-
–
y
wideꢀarrayꢀofꢀnitroalkenesꢀ(Tableꢀ2).ꢀNitrostyrenesꢀpossessingꢀ trifluoro,ꢀ allyl,ꢀ andꢀ propargylꢀ groupsꢀ wereꢀ usedꢀ underꢀ theꢀ
anꢀ electron-donatingꢀ Meꢀ orꢀ MeOꢀ groupꢀ asꢀ wellꢀ asꢀ aꢀ weaklyꢀ optimizedꢀ reactionꢀ conditions,ꢀ complexꢀ mixturesꢀ withꢀ lowꢀ
electron-withdrawingꢀ Clꢀ orꢀ Brꢀ groupꢀ onꢀ theꢀ aromaticꢀ ringꢀ yieldsꢀofꢀtheꢀtargetꢀproductsꢀ3w–yꢀwereꢀobtainedꢀ(entriesꢀ9–11).ꢀ
efficientlyꢀunderwentꢀtheꢀreactionꢀ(entriesꢀ1–7).ꢀOnꢀtheꢀotherꢀ Thisꢀproblemꢀwasꢀeasilyꢀaddressedꢀbyꢀconductingꢀtheꢀreactionꢀ
hand,ꢀβ-nitrostyreneꢀ1hꢀwithꢀaꢀstronglyꢀelectron-withdrawingꢀ atꢀaꢀlowerꢀtemperature.ꢀGratifyingly,ꢀtheꢀtoleranceꢀofꢀtheꢀallylꢀ
CNꢀgroupꢀaffordedꢀtheꢀcorrespondingꢀetherꢀinꢀaꢀrelativelyꢀlowꢀ andꢀ propargylꢀ groupsꢀ allowedꢀ forꢀ furtherꢀ chemicalꢀ
2
yield,ꢀ andꢀ theꢀ introductionꢀ ofꢀ aꢀ NO ꢀ groupꢀ ledꢀ toꢀ aꢀ complexꢀ transformations.ꢀ Theꢀ feasibilityꢀ ofꢀ usingꢀ aꢀ phenolꢀ inꢀ thisꢀ
mixtureꢀ (entriesꢀ 8ꢀ andꢀ 9).ꢀ Additionally,ꢀ theꢀ bulkyꢀ transformationꢀ wasꢀ alsoꢀ examined;ꢀ however,ꢀ aꢀ complexꢀ
naphthylnitroalkeneꢀ 1jꢀ withꢀ extendedꢀ conjugationꢀ smoothlyꢀ mixtureꢀwasꢀobtainedꢀwithoutꢀanyꢀtraceꢀofꢀ3zꢀ(entryꢀ12).ꢀ
underwentꢀdichloro-methoxylationꢀtoꢀfurnishꢀ3jꢀinꢀaꢀgoodꢀyield.ꢀ
Tableꢀ3ꢀStudyꢀonꢀtheꢀalcoholꢀscopeꢀ
Whileꢀnitroalkenesꢀwithꢀelectron-richꢀthienylꢀandꢀfurylꢀgroupsꢀ
affordedꢀtheꢀcorrespondingꢀethersꢀinꢀgoodꢀyields,ꢀtheꢀreactionꢀ
ofꢀ1mꢀgaveꢀtheꢀdichloro-methoxylatedꢀpyridineꢀ3mꢀinꢀreducedꢀ
yieldꢀ (entriesꢀ 10–13).ꢀ Whenꢀ conjugatedꢀ nitroalkeneꢀ 1nꢀ wasꢀ
subjectedꢀ toꢀ thisꢀ protocol,ꢀ theꢀ dichloro-methoxylationꢀ
regioselectivelyꢀ proceededꢀ atꢀ theꢀ doubleꢀ bondꢀ ofꢀ theꢀ
nitroalkene,ꢀfurnishingꢀ3nꢀinꢀ81%ꢀyieldꢀ(entryꢀ14).ꢀThisꢀprotocolꢀ
wasꢀalsoꢀamenableꢀtoꢀaliphaticꢀnitroalkeneꢀ1o,ꢀaffordingꢀetherꢀ
ꢀinꢀ71%ꢀyieldꢀ(entryꢀ15).ꢀ
1
ꢀ a
Entryꢀ
R ꢀ
Temp.ꢀ(°C)ꢀ
Productꢀ
3aꢀ
Yield ꢀ(%)ꢀ
3
o
1
ꢀ
Meꢀ
Etꢀ
rtꢀ
rtꢀ
rtꢀ
rtꢀ
90ꢀ
80ꢀ
75ꢀ
83ꢀ
49ꢀ
45ꢀ
42ꢀ
Tableꢀ2ꢀDichloromethoxylationꢀofꢀvariousꢀnitroalkenesꢀ
2ꢀ
3pꢀ
3qꢀ
3rꢀ
3
4
5
6
7
8
9
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Prꢀ
4-MeOC
6
H
4
CH
2
ꢀ
c
C
6
H
5
CH
2
CH
2
ꢀ
rt ꢀ
3sꢀ
c
3-methylbutylꢀ
i-Prꢀ
rt ꢀ
3tꢀ
rtꢀ
rtꢀ
3uꢀ
3vꢀ
b
t-Buꢀ
c.m. ꢀ
ꢀ a
CF
allylꢀ
propargylꢀ
3
CH
2
ꢀ
ꢀ-10ꢀ
ꢀ-10ꢀ
ꢀ-10ꢀ
rtꢀ
3wꢀ
3xꢀ
46ꢀ
72ꢀ
45ꢀ
Entryꢀ
Rꢀ
ꢀ
aꢀ
bꢀ
cꢀ
dꢀ
eꢀ
fꢀ
Yield ꢀ(%)ꢀ
1
1
1
0ꢀ
1ꢀ
2ꢀ
1
2
3
4
5
6
7
8
9
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
4-MeC
6
H
4
ꢀ
90ꢀ
89ꢀ
76ꢀ
79ꢀ
75ꢀ
73ꢀ
65ꢀ
42ꢀ
3yꢀ
4-MeOC
2-MeOC
6
6
2
H
H
4
ꢀ
ꢀ
b
C
6
H
5
ꢀ
3zꢀ
c.m. ꢀ
4
3,5-(MeO)
C
6
H
3
ꢀ
a
b
c
Isolatedꢀ yield.ꢀ Complexꢀ mixture.ꢀ Sodiumꢀ alkoxidesꢀ wereꢀ preparedꢀ uponꢀ
treatmentꢀofꢀalcoholsꢀ(5.0ꢀequiv.)ꢀwithꢀNaHꢀ(1.2ꢀequiv.)ꢀatꢀ70 °Cꢀforꢀ30ꢀmin,ꢀandꢀ
thenꢀwereꢀreactedꢀwithꢀ1aꢀandꢀNCSꢀinꢀCH Cl2ꢀatꢀroomꢀtemperature.ꢀꢀ
6 5
C H ꢀ
4-BrC
4-ClC
4-NCC
4-O NC
6
H
4
ꢀ
2
6
H
4
ꢀ
gꢀ
hꢀ
iꢀ
6
H
4
ꢀ
Inꢀ orderꢀ toꢀ expandꢀ theꢀ scopeꢀ ofꢀ thisꢀ protocol,ꢀ otherꢀ
halogenatingꢀ reagentsꢀ wereꢀ alsoꢀ employedꢀ (Schemeꢀ 1).ꢀ Theꢀ
reactionꢀ usingꢀ NBSꢀ affordedꢀ β,β-dibromo-β-nitroethylꢀ methylꢀ
etherꢀ4aꢀinꢀexcellentꢀyield.ꢀHowever,ꢀdiiodo-methoxylationꢀdidꢀ
b
2
6
H
4
ꢀ
c.m. ꢀ
1
1
1
1
1
1
0ꢀ
1ꢀ
2ꢀ
3ꢀ
4ꢀ
5ꢀ
2-naphthylꢀ
2-thienylꢀ
2-furylꢀ
jꢀ
62ꢀ
75ꢀ
71ꢀ
36ꢀ
81ꢀ
71ꢀ
kꢀ
lꢀ
notꢀoccurꢀinꢀtheꢀcaseꢀofꢀNIS.ꢀInstead,ꢀmonoiodinatedꢀproductꢀ6a
ꢀ
3-pyridylꢀ
PhCH=CHꢀ
mꢀ
nꢀ
oꢀ
andꢀ protonatedꢀ productꢀ 7aꢀ wereꢀ obtainedꢀ inꢀ 35%ꢀ andꢀ 15%ꢀ
yields,ꢀ respectively,ꢀ whichꢀ mightꢀ beꢀ dueꢀ toꢀ theꢀ higherꢀ stericꢀ
hindranceꢀofꢀtheꢀiodoꢀgroupꢀthanꢀthatꢀofꢀtheꢀbromoꢀgroup.ꢀInꢀ
theꢀ caseꢀ ofꢀ N-fluorobenzenesulfonimide,ꢀ aꢀ smallꢀ amountꢀ ofꢀ
monofluorinatedꢀ productꢀ 9aꢀ wasꢀ obtainedꢀ withoutꢀ anyꢀ
detectableꢀdifluorinatedꢀproductꢀ8a.ꢀWhenꢀaꢀmixtureꢀofꢀNCSꢀꢀ
2 2
PhCH CH ꢀ
a
b
Isolatedꢀyield.ꢀ Complexꢀmixture.ꢀ
ꢀ
ꢀ
ꢀ
2
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
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O rP gl ea na si ce &ꢀ d Bo i ꢀon mo to ꢀ al e dc juu l sa tr ꢀ mC haer mg i ins ts rꢀ y
View Article Online
DOI: 10.1039/C8OB00408K
JournalꢀNameꢀ
ARTICLEꢀ
ꢀ
MeOH 2a (2.0 equiv.)
NBS (2.1 equiv.)
NaH (1.2 equiv.)
MeO
NO
Br
Br
2
CH Cl , rt, 5 h
2
2
4
a (85%)
MeOH 2a (2.0 equiv.)
Reagent (2.1 equiv.)
NaH (1.2 equiv.)
MeO
NO2
I
MeO
NO2
MeO
NO2
H
I
I
+
+
CH Cl , rt, 5 h
2
2
5
a
6a
7a
7a
NO2
Reagent
Yield/%
5
a
6a
NIS
I2
0
35
72
65
15
0
0
0
1
a
ICl
0
MeOH 2a (2.0 equiv.)
(
PhSO ) NF (2.1 equiv.)
MeO
NO
F
2
MeO
NO2
F
2
2
NaH (1.2 equiv.)
F
+
CH Cl , rt, 5 h
2
2
8
a (0%)
9a (17%)
MeOH 2a (2.0 equiv.)
NBS (1.05 equiv.)
NCS (1.05 equiv.)
NaH (1.2 equiv.)
MeO
NO
Cl
Cl
MeO
NO
Br
MeO
NO2
Cl
2
2
+
+
Br
Br
CH Cl , rt, 5 h
2
2
3
a (14%)
4a (34%)
1
0a (52%)
ꢀ
Schemeꢀ1ꢀReactionsꢀinvolvingꢀvariousꢀhalogenatingꢀreagentsꢀ
andꢀ NBSꢀ wasꢀ used,ꢀ dichlorinatedꢀ productꢀ 3a,ꢀ dibrominatedꢀ
productꢀ 4a,ꢀ andꢀ chloro-brominatedꢀ productꢀ 10aꢀ wereꢀ
furnishedꢀ inꢀ 14:34:52ꢀ ratio.ꢀ However,ꢀ 10aꢀ couldꢀ notꢀ beꢀ
isolatedꢀfromꢀtheꢀreactionꢀmixtureꢀdespiteꢀseveralꢀattempts,ꢀ
owingꢀtoꢀtheꢀsimilarꢀpropertiesꢀwithꢀ3aꢀandꢀ4a.ꢀInꢀadditionꢀtoꢀ
theꢀ abovementionedꢀ N-haloamides,ꢀ otherꢀ halogenatingꢀ
reagentsꢀ wereꢀ alsoꢀ scannedꢀ inꢀ thisꢀ reaction.ꢀ Whileꢀ sodiumꢀ
hypochloriteꢀhydrateꢀyieldedꢀdichlorinatedꢀproductꢀ3aꢀinꢀ75%ꢀ
yield,ꢀiodineꢀandꢀiodineꢀmonochlorideꢀincreasedꢀtheꢀyieldꢀofꢀ
mono-iodinatedꢀ productꢀ 6aꢀ toꢀ 72%ꢀ andꢀ 65%ꢀ yields,ꢀ
respectively.ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ3ꢀꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

O rP gl ea na si ce &ꢀ d Bo i ꢀon mo to ꢀ al e dc juu l sa tr ꢀ mC haer mg i ins ts rꢀ y
Page 4 of 8
ARTICLEꢀ
JournalꢀNameꢀ
presenceꢀofꢀazobis(isobutyronitrile)ꢀ(AIBN)ꢀaffordedꢀallylatedꢀ
View Article Online
OMe O
N
14
productꢀ14ꢀinꢀ55%ꢀyield, ꢀleadingꢀtoꢀaꢀextendedꢀstructureꢀwithꢀ
DOI: 10.1039/C8OB00408K
NO2
MeO
O
aꢀ chloronitrometheneꢀ groupꢀ existingꢀ inꢀ aꢀ varietyꢀ ofꢀ
d,e,15ꢀ
1
O
pharmaceuticalsꢀ (Schemeꢀ 3). Moreover,ꢀ 3aꢀ underwentꢀ
eliminationꢀ ofꢀ nitrousꢀ acidꢀ uponꢀ treatmentꢀ withꢀ sodiumꢀ
Cl
1
a
11
N
methoxideꢀtoꢀfurnishꢀ1,1-dichloro-2-methoxyetheneꢀ15ꢀwhichꢀ
canꢀ beꢀ furtherꢀ convertedꢀ intoꢀ otherꢀ usefulꢀ compoundsꢀ
O
O
16
Schemeꢀ4). ꢀ
(
OMe O
N
N
OMe
O
Conclusionsꢀ
O
O
H
Cl
Cl
NO2
Aꢀfacileꢀandꢀefficientꢀapproachꢀtoꢀβ,β-dihalo-β-nitroethylꢀalkylꢀ
ethersꢀ wasꢀ developedꢀ uponꢀ treatmentꢀ ofꢀ nitroalkenesꢀ withꢀ
alcoholsꢀ andꢀ N-halosuccinimidesꢀ inꢀ theꢀ presenceꢀ ofꢀ sodiumꢀ
hydrideꢀ underꢀ mildꢀ conditions.ꢀ Theꢀ syntheticꢀ utilityꢀ wasꢀ
demonstratedꢀbyꢀtheꢀtransformationꢀofꢀtheꢀobtainedꢀetherꢀ3aꢀ
intoꢀ otherꢀ usefulꢀ compoundsꢀ throughꢀ allylationꢀ ofꢀ theꢀ
dihalo(nitro)methylꢀ groupꢀ andꢀ eliminationꢀ ofꢀ nitrousꢀ acid,ꢀ
respectively.ꢀ Furtherꢀ effortsꢀ aboutꢀ theꢀ applicationꢀ ofꢀ thisꢀ
protocolꢀforꢀpreparingꢀversatileꢀfunctionalizedꢀcompoundsꢀareꢀ
ongoingꢀinꢀourꢀgroup.ꢀ
N
Cl
1
3
1
2
O
OMe
NO2
Cl
Cl
3
a
ꢀ
Schemeꢀ2ꢀAꢀplausibleꢀmechanismꢀforꢀtheꢀformationꢀofꢀ3a
ꢀ
Onꢀtheꢀbasisꢀofꢀtheꢀaboveꢀresults,ꢀaꢀplausibleꢀmechanismꢀforꢀ
theꢀdihalo-alkoxylationꢀisꢀproposedꢀ(Schemeꢀ2).ꢀTheꢀconjugateꢀ
additionꢀ ofꢀ sodiumꢀ methoxideꢀ generatedꢀ inꢀ situꢀ fromꢀ
methanolꢀ 2a,ꢀ toꢀ nitrostyreneꢀ 1aꢀ affordsꢀ nitronateꢀ 11.ꢀ Theꢀ
reactionꢀofꢀ11ꢀwithꢀNCSꢀfacilitatesꢀchlorinationꢀbyꢀnucleophilicꢀ
substitution,ꢀaffordingꢀmono-chlorinatedꢀintermediateꢀ12.ꢀTheꢀ
subsequentꢀdeprotonationꢀandꢀchlorinationꢀofꢀ13ꢀleadsꢀtoꢀtheꢀ
formationꢀ ofꢀ β,β-dihalo-β-nitroethylꢀ alkylꢀ etherꢀ 3a.ꢀ Anotherꢀ
reactionꢀmechanismꢀincludingꢀaꢀsingle-electronꢀtransferꢀfromꢀ
nitronateꢀ toꢀ NCSꢀ isꢀ alsoꢀ acceptable.ꢀ Whenꢀ p-nitrophenylꢀ
substrateꢀ 1iꢀ wasꢀ used,ꢀ noꢀ targetꢀ productꢀ 3iꢀ wasꢀ notꢀ beꢀ
detectedꢀ (Tableꢀ 2,ꢀ entryꢀ 9).ꢀ Sinceꢀ thereꢀ isꢀ aꢀ possibilityꢀ thatꢀ
goodꢀ electronꢀ acceptorꢀ 1iꢀ inhibitedꢀ theꢀ single-electronꢀ
transfer,ꢀtheꢀlatterꢀmechanismꢀcouldꢀnotꢀbeꢀexcluded.ꢀ
Experimentalꢀ
Experimentalꢀsectionꢀ
Theꢀ meltingꢀ pointsꢀ wereꢀ determinedꢀ onꢀ SRS-Optimeltꢀ
AutomatedꢀMeltingꢀPointꢀSystem,ꢀandꢀwereꢀuncorrected.ꢀAllꢀ
theꢀ reagentsꢀ andꢀ solventsꢀ wereꢀ commerciallyꢀ availableꢀ andꢀ
1
usedꢀasꢀreceived.ꢀTheꢀ HꢀNMRꢀspectraꢀwereꢀmeasuredꢀonꢀaꢀ
BrukerꢀAscend-400ꢀatꢀ400ꢀMHzꢀwithꢀtetramethylsilaneꢀasꢀanꢀ
1
internalꢀstandard.ꢀTheꢀ CꢀNMRꢀspectraꢀwereꢀmeasuredꢀonꢀaꢀ
3
1
3
BrukerꢀAscend-400ꢀatꢀ100ꢀMHz,ꢀandꢀassignmentsꢀofꢀ CꢀNMRꢀ
spectraꢀ wereꢀ performedꢀ byꢀ DEPTꢀ experiments.ꢀ Theꢀ high-
resolutionꢀmassꢀspectraꢀwereꢀmeasuredꢀonꢀanꢀABꢀSCIEXꢀTripleꢀ
TOFꢀ 4600.ꢀ Theꢀ IRꢀ spectraꢀ wereꢀ recordedꢀ onꢀ aꢀ JASCOꢀ FT/IR-
4
200ꢀspectrometer.ꢀ
Bu Sn
3
Generalꢀprocedureꢀforꢀtheꢀpreparationꢀofꢀnitroalkenesꢀ
MeO
NO2
Cl AIBN (0.48 equiv.)
Cl
(2.5 equiv.)
MeO
NO2
(E)-Aromaticꢀnitroalkenesꢀ1a–nꢀwereꢀsynthesizedꢀinꢀmoderateꢀ
toꢀ goodꢀ yieldsꢀ uponꢀ treatmentꢀ ofꢀ aromaticꢀ aldehydesꢀ withꢀ
Cl
Toluene, 120 °C, 9 h
1
7
nitromethaneꢀ inꢀ theꢀ presenceꢀ ofꢀ ammoniumꢀ acetate. ꢀ
Aliphaticꢀ nitroalkeneꢀ 1oꢀ wasꢀ preparedꢀ throughꢀ theꢀ
condensationꢀ reactionꢀ ofꢀ aliphaticꢀ aldehydeꢀ withꢀ
nitromethaneꢀinꢀtheꢀpresenceꢀofꢀsodiumꢀhydroxideꢀfollowedꢀ
3
Schemeꢀ3ꢀAllylationꢀofꢀ3a
a
14 (55%)
ꢀ
ꢀ
1
8
byꢀMsCl–mediatedꢀdehydration. ꢀ
Generalꢀprocedureꢀforꢀone-potꢀsynthesisꢀofꢀβ,β-dihalo-β-nitroet-ꢀ
hylꢀalkylꢀethersꢀ3ꢀ
1
-(2,2-Dichloro-1-methoxy-2-nitroethyl)-4-methylbenzeneꢀ
3a).ꢀ Toꢀ aꢀ solutionꢀ ofꢀ sodiumꢀ hydrideꢀ (60%ꢀ dispersionꢀ inꢀ
mineralꢀ oil,ꢀ 14.7ꢀ mg,ꢀ 0.37ꢀ mmol)ꢀ inꢀ CH Cl ꢀ (1.7ꢀ mL),ꢀ wereꢀ
addedꢀMeOHꢀ2aꢀ(24.9ꢀ L,ꢀ0.61ꢀmmol),ꢀ(E)-β-nitrostyreneꢀ1aꢀ
50.0ꢀ mg,ꢀ 0.31ꢀ mmol),ꢀ andꢀ NCSꢀ (86.0ꢀ mg,ꢀ 0.64ꢀ mmol)ꢀ
(
2
2
ꢀ
µ
Schemeꢀ4ꢀEliminationꢀofꢀnitrousꢀacidꢀfromꢀ3a
ꢀ
(
successively.ꢀ Theꢀ resultantꢀ mixtureꢀ wasꢀ stirredꢀ atꢀ roomꢀ
temperatureꢀ forꢀ 5ꢀ h.ꢀ Then,ꢀ theꢀ solventꢀ wasꢀ evaporatedꢀ toꢀ
affordꢀaꢀreactionꢀmixtureꢀasꢀaꢀyellowꢀoil,ꢀwhichꢀwasꢀtreatedꢀbyꢀ
columnꢀchromatographyꢀonꢀsilicaꢀgelꢀtoꢀaffordꢀβ,β-dichloro-β-
Finally,ꢀtoꢀillustrateꢀtheꢀsyntheticꢀpotentialꢀofꢀthisꢀprotocol,ꢀtheꢀ
convertionꢀ ofꢀ theꢀ resultantꢀ ethersꢀ ꢀ possessingꢀ aꢀ
dihalo(nitro)methylꢀ groupꢀ intoꢀ otherꢀ usefulꢀ buildingꢀ blocksꢀ
3
wasꢀinvestigated.ꢀTheꢀreactionꢀofꢀ3aꢀwithꢀallyltributyltinꢀinꢀtheꢀ
4
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 5 of 8
O rP gl ea na si ce &ꢀ d Bo i ꢀon mo to ꢀ al e dc juu l sa tr ꢀ mC haer mg i ins ts rꢀ y
JournalꢀNameꢀ
ꢀARTICLEꢀ
nitroethylꢀmethylꢀetherꢀ3aꢀ(elutedꢀwithꢀCH
2.0ꢀ mg,ꢀ 0.27ꢀ mmol,ꢀ 90%ꢀ yield)ꢀ asꢀ aꢀ colorlessꢀ oil.ꢀ Hꢀ NMRꢀ
DMSO-d ,ꢀ400ꢀMHz)ꢀδꢀ2.28ꢀ(s,ꢀ3H),ꢀ3.15ꢀ(s,ꢀ3H),ꢀ5.37ꢀ(s,ꢀ1H),ꢀ
2
Cl
2
/hexaneꢀ=ꢀ1/5,ꢀ
4-(2,2-Dichloro-1-methoxy-2-nitroethyl)benzonitrileꢀ
(3h).ꢀ
View Article Online
1
1
Colorlessꢀoilꢀ(35.2ꢀmg,ꢀ0.13ꢀmmol,ꢀ42%).ꢀ HꢀNMRꢀ(CDCl
DOI: 10.1039/C8OB00408K
7
3
,ꢀ400ꢀ
(
6
MHz)ꢀδꢀ3.34ꢀ(s,ꢀ3H),ꢀ5.29ꢀ(s,ꢀ1H),ꢀ7.71ꢀ(d,ꢀJꢀ=ꢀ8.4ꢀHz,ꢀ2H),ꢀ7.75ꢀ
13
1
3
7
d
1
1
2
.22ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H),ꢀ7.39ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(DMSO-
,,ꢀ100ꢀMHz)ꢀδꢀ20.8ꢀ(CH ),ꢀ57.5ꢀ(CH ),ꢀ86.1ꢀ(CH),ꢀ114.6ꢀ(C),ꢀ
28.6ꢀ(C),ꢀ128.8ꢀ(CH),ꢀ129.4ꢀ(CH),ꢀ139.5ꢀ(C);ꢀ IRꢀ(ATR/cm )ꢀ
(d,ꢀJꢀ=ꢀ8.4ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
(CH),ꢀ113.4ꢀ(C),ꢀ114.2ꢀ(C),ꢀ118.1ꢀ(C),ꢀ130.2ꢀ(CH),ꢀ132.1ꢀ(CH),ꢀ
3 3
,ꢀ100ꢀMHz)ꢀδꢀ58.6ꢀ(CH ),ꢀ86.9ꢀ
6
3
3
-
1
-1
137.2ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀ
ν
ꢀ
νꢀ1341,ꢀ1587,ꢀ2232;ꢀHRMSꢀ(ESI/TOF)ꢀ
+
+
330,ꢀ1587;ꢀHRMSꢀ(ESI/TOF)ꢀCalcdꢀforꢀC10
H
12Cl
2
NO
3
ꢀ[(M+H) ]:ꢀ
CalcdꢀforꢀC10 Cl ꢀ[(M+H) ]:ꢀ274.9985,ꢀfoundꢀ274.9973.ꢀꢀꢀꢀ
H
9
2 2 3
N O
64.0189,ꢀfoundꢀ264.0187.ꢀꢀꢀꢀ
1
2-(2,2-Dichloro-1-methoxy-2-nitroethyl)naphthaleneꢀ
1
Colorlessꢀoilꢀ(56.4ꢀmg,ꢀ0.19ꢀmmol,ꢀ62%).ꢀ HꢀNMRꢀ(CDCl
(3j).
,ꢀ400ꢀ
ꢀ
Whenꢀ otherꢀ nitroalkenesꢀ
,ꢀ alcoholsꢀ
2
,ꢀ andꢀ halogenatingꢀ
3
reagentsꢀwereꢀused,ꢀexperimentsꢀwereꢀconductedꢀinꢀaꢀsimilarꢀ
way.ꢀ
MHz)ꢀδꢀ3.35ꢀ(s,ꢀ3H),ꢀ5.39ꢀ(s,ꢀ1H),ꢀ7.52–7.57ꢀ(m,ꢀ2H),ꢀ7.67ꢀ(dd,ꢀJꢀ
1
3
=ꢀ1.6,ꢀ8.8ꢀHz,ꢀ1H),ꢀ7.87–7.91ꢀ(m,ꢀ3H),ꢀ8.03ꢀ(s,ꢀ1H);ꢀ CꢀNMRꢀ
(CDCl ,ꢀ100ꢀMHz)ꢀδꢀ58.2ꢀ(CH ),ꢀ87.8ꢀ(CH),ꢀ114.6ꢀ(C),ꢀ125.9ꢀ(CH),ꢀ
126.6ꢀ (CH),ꢀ 127.2ꢀ (CH),ꢀ 127.8ꢀ (CH),ꢀ 128.1ꢀ (CH),ꢀ 128.4ꢀ (CH),ꢀ
1
-(2,2-Dichloro-1-methoxy-2-nitroethyl)-4-methoxybenzeneꢀ
3
3
1
3b).ꢀColorlessꢀoilꢀ(75.9ꢀmg,ꢀ0.27ꢀmmol,ꢀ89%).ꢀ HꢀNMRꢀ(CDCl
(
3
,ꢀ
-
1
4
8
00ꢀMHz)ꢀδꢀ3.29ꢀ(s,ꢀ3H),ꢀ3.84ꢀ(s,ꢀ3H),ꢀ5.16ꢀ(s,ꢀ1H),ꢀ6.96ꢀ(d,ꢀJꢀ=ꢀ
129.3ꢀ(C),ꢀ130.0ꢀ(CH),ꢀ132.7ꢀ(C),ꢀ134.1ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀνꢀ1340,ꢀ
+
1
3
.8ꢀHz,ꢀ2H),ꢀ7.47ꢀ(d,ꢀJꢀ=ꢀ8.8ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
),ꢀ57.9ꢀ(CH ),ꢀ87.4ꢀ(CH),ꢀ113.8ꢀ(CH),ꢀ114.8ꢀ(C),ꢀ123.5ꢀ
C),ꢀ130.8ꢀ(CH),ꢀ161.0ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀ
ESI/TOF)ꢀ Calcdꢀ forꢀ C10 NO Naꢀ [(M+Na) ]:ꢀ 301.9957,ꢀ
3
,ꢀ100ꢀMHz)ꢀ
1587;ꢀ HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ C13
322.0008,ꢀfoundꢀ322.0017.ꢀꢀꢀꢀ
2-(2,2-Dichloro-1-methoxy-2-nitroethyl)thiopheneꢀ
2 3
H11Cl NO Naꢀ [(M+Na) ]:ꢀ
δꢀ55.3ꢀ(CH
3
3
-
1
(
(
ν
ꢀ1330,ꢀ1585;ꢀHRMSꢀ
(3k).ꢀ
,ꢀ400ꢀ
MHz)ꢀδꢀ3.37ꢀ(s,ꢀ3H),ꢀ5.49ꢀ(s,ꢀ1H),ꢀ7.08ꢀ(dd,ꢀJꢀ=ꢀ4.0,ꢀ4.8ꢀHz,ꢀ1H),ꢀ
+
1
H
11Cl
2
4
Colorlessꢀoilꢀ(58.6ꢀmg,ꢀ0.23ꢀmmol,ꢀ75%).ꢀ HꢀNMRꢀ(CDCl
3
foundꢀ301.9960.ꢀꢀ
-(2,2-Dichloro-1-methoxy-2-nitroethyl)-2-methoxybenzeneꢀ
1
3
1
7.30ꢀ(d,ꢀJꢀ=ꢀ4.0ꢀHz,ꢀ1H),ꢀ7.47ꢀ(d,ꢀJꢀ=ꢀ4.8ꢀHz,ꢀ1H);ꢀ CꢀNMRꢀ(CDCl
100ꢀMHz)ꢀδꢀ58.3ꢀ(CH ),ꢀ84.6ꢀ(CH),ꢀ113.9ꢀ(C),ꢀ126.7ꢀ(CH),ꢀ128.4ꢀ
(CH),ꢀ130.4ꢀ(CH),ꢀ134.4ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀνꢀ1333,ꢀ1586;ꢀHRMSꢀ
3
,ꢀ
1
3c).ꢀColorlessꢀoilꢀ(64.5ꢀmg,ꢀ0.23ꢀmmol,ꢀ76%).ꢀ HꢀNMRꢀ(CDCl
(
3
,ꢀ
3
-
1
4
8
00ꢀMHz)ꢀδꢀ3.25ꢀ(s,ꢀ3H),ꢀ3.88ꢀ(s,ꢀ3H),ꢀ5.91ꢀ(s,ꢀ1H),ꢀ6.96ꢀ(d,ꢀJꢀ=ꢀ
.0ꢀHz,ꢀ1H),ꢀ7.05ꢀ(dd,ꢀJꢀ=ꢀ8.0,ꢀ8.0ꢀHz,ꢀ1H),ꢀ7.41ꢀ(dd,ꢀJꢀ=ꢀ8.0,ꢀ8.0ꢀ
+
(ESI/TOF)ꢀ Calcdꢀ forꢀ C
255.9604.ꢀꢀꢀꢀ
7 8 2 3
H Cl NO Sꢀ [(M+H) ]:ꢀ 255.9597,ꢀ foundꢀ
1
3
Hz,ꢀ1H),ꢀ7.62ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ1H);ꢀ CꢀNMRꢀ(CDCl
5.5ꢀ(CH ),ꢀ57.8ꢀ(CH ),ꢀ79.8ꢀ(CH),ꢀ110.7ꢀ(CH),ꢀ115.0ꢀ(C),ꢀ120.5ꢀ
C),ꢀ120.6ꢀ(CH),ꢀ129.6ꢀ(CH),ꢀ131.1ꢀ(CH),ꢀ158.8ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀ
ꢀ 1337,ꢀ 1585;ꢀ HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ C10 NO Naꢀ
3
,ꢀ100ꢀMHz)ꢀδꢀ
5
3
3
2-(2,2-Dichloro-1-methoxy-2-nitroethyl)furanꢀ (3l).ꢀ Colorlessꢀ
1
oilꢀ(51.9ꢀmg,ꢀ0.22ꢀmmol,ꢀ71%).ꢀ HꢀNMRꢀ(CDCl
-
1
(
3
,ꢀ400ꢀMHz)ꢀδꢀ3.36ꢀ
ν
H
11Cl
2
4
(s,ꢀ3H),ꢀ5.33ꢀ(s,ꢀ1H),ꢀ6.48ꢀ(dd,ꢀJꢀ=ꢀ1.6,ꢀ3.2ꢀHz,ꢀ1H),ꢀ6.69ꢀ(d,ꢀJꢀ=ꢀ
+
13
[
(M+Na) ]:ꢀ301.9957,ꢀfoundꢀ301.9959.ꢀ
-(2,2-Dichloro-1-methoxy-2-nitroethyl)-3,5-dimethoxyben-ꢀ
3.2ꢀHz,ꢀ1H),ꢀ7.53ꢀ(d,ꢀJꢀ=ꢀ1.6ꢀHz,ꢀ1H);ꢀ CꢀNMRꢀ(CDCl
δꢀ58.3ꢀ(CH ),ꢀ82.3ꢀ(CH),ꢀ110.8ꢀ(CH),ꢀ112.6ꢀ(C),ꢀ112.7ꢀ(CH),ꢀ144.3ꢀ
(CH),ꢀ146.0ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀ
3
,ꢀ100ꢀMHz)ꢀ
1
3
1
zeneꢀ(3d).ꢀColorlessꢀoilꢀ(74.2ꢀmg,ꢀ0.24ꢀmmol,ꢀ79%).ꢀ HꢀNMRꢀ
-1
ν
ꢀ1334,ꢀ1587;ꢀHRMSꢀ(ESI/TOF)ꢀ
+
(
(
CDCl3,ꢀ400ꢀMHz)ꢀδꢀ3.33ꢀ(s,ꢀ3H),ꢀ3.82ꢀ(s,ꢀ6H),ꢀ5.13ꢀ(s,ꢀ1H),ꢀ6.54ꢀ
CalcdꢀforꢀC H Cl NO ꢀ[(M+H) ]:ꢀ239.9825,ꢀfoundꢀ239.9827.ꢀꢀꢀꢀꢀ
7 8 2 4
1
3
t,ꢀJꢀ=ꢀ2.4ꢀHz,ꢀ1H),ꢀ6.70ꢀ(d,ꢀJꢀ=ꢀ2.4ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
),ꢀ55.5ꢀ(CH ),ꢀ58.2ꢀ(CH ),ꢀ87.6ꢀ(CH),ꢀ101.7ꢀ(CH),ꢀ
07.7ꢀ(CH),ꢀ114.4ꢀ(C),ꢀ134.0ꢀ(C),ꢀ160.6ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀ
3
,ꢀ100ꢀ
2-(2,2-Dichloro-1-methoxy-2-nitroethyl)pyridineꢀ
(3m).ꢀ
,ꢀ400ꢀ
MHz)ꢀδꢀ3.35ꢀ(s,ꢀ3H),ꢀ5.28ꢀ(s,ꢀ1H),ꢀ7.41ꢀ(dd,ꢀJꢀ=ꢀ4.8,ꢀ8.0ꢀHz,ꢀ1H),ꢀ
1
MHz)ꢀδꢀ55.5ꢀ(CH
3
3
3
Colorlessꢀoilꢀ(27.6ꢀmg,ꢀ0.11ꢀmmol,ꢀ36%).ꢀ HꢀNMRꢀ(CDCl
3
-
1
1
1
3
ν
ꢀ1318,ꢀ
+
13
586;ꢀ HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ C11
32.0063,ꢀfoundꢀ332.0068.ꢀ
H
13Cl
2
NO
5
Naꢀ [(M+Na) ]:ꢀ
7.93ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ1H),ꢀ8.71ꢀ(d,ꢀJꢀ=ꢀ4.8ꢀHz,ꢀ1H),ꢀ8.80ꢀ(s,ꢀ1H);ꢀ Cꢀ
NMRꢀ(CDCl
3 3
,ꢀ100ꢀMHz)ꢀδꢀ58.5ꢀ(CH ),ꢀ85.8ꢀ(CH),ꢀ113.7ꢀ(C),ꢀ123.3ꢀ
-
(
2,2-Dichloro-1-methoxy-2-nitroethyl)benzeneꢀ
(3e).
,ꢀ400ꢀ
MHz)ꢀδꢀ3.31ꢀ(s,ꢀ3H),ꢀ5.21ꢀ(s,ꢀ1H),ꢀ7.43–7.45ꢀ(m,ꢀ3H),ꢀ7.55–7.57ꢀ
ꢀ
(CH),ꢀ128.0ꢀ(C),ꢀ136.7ꢀ(CH),ꢀ150.8ꢀ(CH),ꢀ151.3ꢀ(CH);ꢀIRꢀ(ATR/cm
1
1
Colorlessꢀoilꢀ(56.9ꢀmg,ꢀ0.23ꢀmmol,ꢀ75%).ꢀ HꢀNMRꢀ(CDCl
3
)ꢀ
[(M+H) ]:ꢀ250.9985,ꢀfoundꢀ250.9997.ꢀꢀ
(E)-(4,4-Dichloro-3-methoxy-4-nitrobut-1-enyl)benzeneꢀ(3n).ꢀ
8 9 2 2 3ꢀ
νꢀ 1334,ꢀ 1587;ꢀ HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ C H Cl N O
+
1
3
(
m,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
3 3
,ꢀ100ꢀMHz)ꢀδꢀ58.1ꢀ(CH ),ꢀ87.6ꢀ(CH),ꢀ
1
1
14.5ꢀ (C),ꢀ 128.3ꢀ (CH),ꢀ 129.5ꢀ (CH),ꢀ 130.0ꢀ (CH),ꢀ 131.8ꢀ (C);ꢀ IRꢀ
3
Colorlessꢀoilꢀ(68.3ꢀmg,ꢀ0.25ꢀmmol,ꢀ81%).ꢀ HꢀNMRꢀ(CDCl ,ꢀ400ꢀ
-
1
ATR/cm )ꢀ
(
ν
ꢀ 1336,ꢀ 1586;ꢀ HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ
+
MHz)ꢀδꢀ3.40ꢀ(s,ꢀ3H),ꢀ4.73ꢀ(d,ꢀJꢀ=ꢀ7.6ꢀHz,ꢀ1H),ꢀ6.13ꢀ(dd,ꢀJꢀ=ꢀ7.6,ꢀ
16.0ꢀHz,ꢀ1H),ꢀ6.89ꢀ(d,ꢀJꢀ=ꢀ16.0ꢀHz,ꢀ1H),ꢀ7.32–7.40ꢀ(m,ꢀ3H),ꢀ7.47ꢀ
C
9
H
10Cl
2
NO
3
ꢀ[(M+H) ]:ꢀ250.0032,ꢀfoundꢀ250.0031.ꢀꢀꢀ
1
(d,ꢀJꢀ=ꢀ6.8ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
3
1
-Bromo-4-(2,2-dichloro-1-methoxy-2-nitroethyl)benzeneꢀꢀ
3 3
,ꢀ100ꢀMHz)ꢀδꢀ57.8ꢀ(CH ),ꢀ87.6ꢀ
1
3f).ꢀColorlessꢀoilꢀ(72.8ꢀmg,ꢀ0.22ꢀmmol,ꢀ73%).ꢀ HꢀNMRꢀ(CDCl
(
3
,ꢀ
(CH),ꢀ113.6ꢀ(C),ꢀ119.7ꢀ(CH),ꢀ127.1ꢀ(CH),ꢀ128.8ꢀ(CH),ꢀ129.1ꢀ(CH),ꢀ
-
135.1ꢀ (C),ꢀ 139.7ꢀ (CH);ꢀ IRꢀ (ATR/cm )ꢀ νꢀ 1332,ꢀ 1587;ꢀ HRMSꢀ
1
4
7
8
00ꢀMHz)ꢀδꢀ3.31ꢀ(s,ꢀ3H),ꢀ5.18ꢀ(s,ꢀ1H),ꢀ7.44ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H),ꢀ
1
.58ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
3
+
3
,ꢀ100ꢀMHz)ꢀδꢀ58.2ꢀ(CH
7.1ꢀ (CH),ꢀ 113.9ꢀ (C),ꢀ 124.5ꢀ (C),ꢀ 130.9ꢀ (C),ꢀ 131.1ꢀ (CH),ꢀ 131.6ꢀ
3
),ꢀ
(ESI/TOF)ꢀ Calcdꢀ forꢀ C11
276.0187.ꢀꢀ
2 3
H12Cl NO ꢀ [(M+H) ]:ꢀ 276.0189,ꢀ foundꢀ
-
1
(
CH);ꢀ IRꢀ (ATR/cm )ꢀ
H
ν
ꢀ 1336,ꢀ 1587;ꢀ HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ
(4,4-Dichloro-3-methoxy-4-nitrobutyl)benzeneꢀ
1
Colorlessꢀoilꢀ(63.3ꢀmg,ꢀ0.22ꢀmmol,ꢀ71%).ꢀ HꢀNMRꢀ(CDCl
(3o).ꢀ
,ꢀ400ꢀ
+
ꢀ[(M+H) ]:ꢀ327.9137,ꢀfoundꢀ327.9129.ꢀꢀꢀ
C
9
9
BrCl2NO
3
3
1
-Chloro-4-(2,2-dichloro-1-methoxy-2-nitroethyl)benzeneꢀ
MHz)ꢀδꢀ2.03–2.12ꢀ(m,ꢀ1H),ꢀ2.18–2.26ꢀ(m,ꢀ1H),ꢀ2.72–2.80ꢀ(m,ꢀ
1
3g).ꢀColorlessꢀoilꢀ(56.0ꢀmg,ꢀ0.20ꢀmmol,ꢀ65%).ꢀ HꢀNMRꢀ(CDCl
(
3
,ꢀ
1H),ꢀ2.93–3.00ꢀ(m,ꢀ1H),ꢀ3.48ꢀ(s,ꢀ3H),ꢀ4.20ꢀ(dd,ꢀJꢀ=ꢀ2.4,ꢀ9.6ꢀHz,ꢀ
1
3
4
7
8
00ꢀMHz)ꢀδꢀ3.31ꢀ(s,ꢀ3H),ꢀ5.20ꢀ(s,ꢀ1H),ꢀ7.42ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H),ꢀ
,ꢀ100ꢀMHz)ꢀδꢀ58.2ꢀ(CH
1H),ꢀ7.22–7.25ꢀ(m,ꢀ3H),ꢀ7.33ꢀ(dd,ꢀJꢀ=ꢀ7.6,ꢀ7.6ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ
(CDCl ,ꢀ100ꢀMHz)ꢀδꢀ31.9ꢀ(CH ),ꢀ33.1ꢀ(CH ),ꢀ61.4ꢀ(CH ),ꢀ86.8ꢀ(CH),ꢀ
115.1ꢀ (C),ꢀ 126.5ꢀ (CH),ꢀ 128.3ꢀ (CH),ꢀ 128.7ꢀ (CH),ꢀ 140.2ꢀ (C);ꢀ IRꢀ
1
.50ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
3
3
3
),ꢀ
3
2
2
3
7.0ꢀ(CH),ꢀ114.1ꢀ(C),ꢀ128.7ꢀ(CH),ꢀ130.4ꢀ(C),ꢀ130.8ꢀ(CH),ꢀ136.3ꢀ
1
-
-1
(
C);ꢀ IRꢀ (ATR/cm )ꢀ
H
ν
ꢀ 1341,ꢀ 1587;ꢀ HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ
(ATR/cm )ꢀ νꢀ 1327,ꢀ 1583;ꢀ HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ
+
NO Naꢀ[(M+Na) ]:ꢀ300.0165,ꢀfoundꢀ300.0174.ꢀꢀ
+
Cl NO Naꢀ[(M+Na) ]:ꢀ306.9540,ꢀfoundꢀ306.9555.ꢀꢀꢀ
C
9
9
3
3
C
11
H
13Cl
2
3
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ5ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

O rP gl ea na si ce &ꢀ d Bo i ꢀon mo to ꢀ al e dc juu l sa tr ꢀ mC haer mg i ins ts rꢀ y
Page 6 of 8
ARTICLEꢀ
-(2,2-Dichloro-1-ethoxy-2-nitroethyl)-4-methylbenzeneꢀ(3p).ꢀ
JournalꢀNameꢀ
1
View Article Online
2 3
νꢀ 1324,ꢀ 1587;ꢀ HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ C12H15Cl NO Naꢀ
1
+
[(M+Na) ]:ꢀ314.0321,ꢀfoundꢀ314.0331.ꢀꢀ
DOI: 10.1039/C8OB00408K
Colorlessꢀoilꢀ(67.4ꢀmg,ꢀ0.24ꢀmmol,ꢀ80%).ꢀ HꢀNMRꢀ(CDCl
MHz)ꢀδꢀ1.13ꢀ(t,ꢀJꢀ=ꢀ7.2ꢀHz,ꢀ3H),ꢀ2.39ꢀ(s,ꢀ3H),ꢀ3.38–3.45ꢀ(m,ꢀ1H),ꢀ
.47–3.54ꢀ(m,ꢀ1H),ꢀ5.27ꢀ(s,ꢀ1H),ꢀ7.22ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H),ꢀ7.44ꢀ(d,ꢀ
3
,ꢀ400ꢀ
1-[2,2-Dichloro-2-nitro-1-(2,2,2-trifluoroethoxy)ethyl]-4-
methylbenzeneꢀ(3w).ꢀColorlessꢀoilꢀ(46.2ꢀmg,ꢀ0.14ꢀmmol,ꢀ46%).ꢀ
3
1
3
1
Jꢀ=ꢀ8.0ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
CH ),ꢀ66.2ꢀ(CH ),ꢀ85.8ꢀ(CH),ꢀ114.9ꢀ(C),ꢀ129.0ꢀ(CH),ꢀ129.4ꢀ(CH),ꢀ
29.7ꢀ (C),ꢀ 139.9ꢀ (C);ꢀ IRꢀ (ATR/cm )ꢀ
ESI/TOF)ꢀ Calcdꢀ forꢀ C11 NO Naꢀ [(M+Na) ]:ꢀ 300.0165,ꢀ
foundꢀ300.0179.ꢀꢀ
-(2,2-Dichloro-2-nitro-1-propoxyethyl)-4-methylbenzeneꢀ
3
,ꢀ100ꢀMHz)ꢀδꢀ14.8ꢀ(CH
3
),ꢀ21.3ꢀ
HꢀNMRꢀ(CDCl3,ꢀ400ꢀMHz)ꢀδꢀ2.40ꢀ(s,ꢀ3H),ꢀ3.70–3.87ꢀ(m,ꢀ2H),ꢀ
1
3
(
3
2
5.46ꢀ(s,ꢀ1H),ꢀ7.26ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H),ꢀ7.44ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H);ꢀ Cꢀ
NMRꢀ(CDCl ,ꢀ100ꢀMHz)ꢀδꢀ21.3ꢀ(CH ),ꢀ66.8ꢀ(q,ꢀJꢀ=ꢀ35.2ꢀHz,ꢀCH ),ꢀ
86.6ꢀ (CH),ꢀ 113.9ꢀ (C),ꢀ 123.0ꢀ (q,ꢀ Jꢀ =ꢀ 277.0ꢀ Hz,ꢀ CF ),ꢀ 127.3ꢀ (C),ꢀ
ꢀ1331,ꢀ1590;ꢀ
-
1
1
ν
ꢀ 1326,ꢀ 1587;ꢀ HRMSꢀ
3
3
2
+
(
H
13Cl
2
3
3
-
1
129.3ꢀ(CH),ꢀ129.4ꢀ(CH),ꢀ140.9ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀ
ν
+
1
HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ C11
353.9882,ꢀfoundꢀ353.9892.ꢀꢀ
2 3 3
H10Cl F NO Naꢀ [(M+Na) ]:ꢀ
ꢀ
1
(
3q).ꢀColorlessꢀoilꢀ(66.3ꢀmg,ꢀ0.23ꢀmmol,ꢀ75%). HꢀNMRꢀ(CDCl
00ꢀMHz)ꢀδꢀ0.85ꢀ(t,ꢀJꢀ=ꢀ7.2ꢀHz,ꢀ3H),ꢀ1.53ꢀ(ddq,ꢀJꢀ=ꢀ6.4,ꢀ6.4,ꢀ7.2ꢀ
Hz,ꢀ2H),ꢀ2.39ꢀ(s,ꢀ3H),ꢀ3.29ꢀ(dt,ꢀJꢀ=ꢀ6.4,ꢀ13.2ꢀHz,ꢀ1H),ꢀ3.41ꢀ(dt,ꢀJꢀ=ꢀ
3
,ꢀ
4
1-[1-(3-propenyloxy)-2,2-dichloro-2-nitroethyl]-4-methylꢀ
1
benzeneꢀ(3x).ꢀColorlessꢀoilꢀ(63.8ꢀmg,ꢀ0.22ꢀmmol,ꢀ72%).ꢀ HꢀNMRꢀ
6
=
.4,ꢀ13.2ꢀHz,ꢀ1H),ꢀ5.25ꢀ(s,ꢀ1H),ꢀ7.25ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H),ꢀ7.44ꢀ(d,ꢀJꢀ
3
(CDCl ,ꢀ400ꢀMHz)ꢀδꢀ2.39ꢀ(s,ꢀ3H),ꢀ3.82ꢀ(dddd,ꢀJꢀ=ꢀ1.2,ꢀ1.2,ꢀ6.8,ꢀ
1
3
ꢀ8.0ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
),ꢀ22.6ꢀ(CH ),ꢀ72.3ꢀ(CH ),ꢀ86.1ꢀ(CH),ꢀ114.9ꢀ(C),ꢀ128.9ꢀ(CH),ꢀ
29.4ꢀ(CH),ꢀ129.6ꢀ(C),ꢀ139.9ꢀ(C)ꢀ;ꢀIRꢀ(ATR/cm )ꢀ
3
,ꢀ100ꢀMHz)ꢀδꢀ10.3ꢀ(CH
3
),ꢀ21.3ꢀ
12.8ꢀHz,ꢀ1H),ꢀ4.03ꢀ(dddd,ꢀJꢀ=ꢀ1.2,ꢀ1.2,ꢀ5.2,ꢀ12.8ꢀHz,ꢀ1H),ꢀ5.15–
5.20ꢀ(m,ꢀ2H),ꢀ5.33ꢀ(s,ꢀ1H),ꢀ5.71–5.81ꢀ(m,ꢀ1H),ꢀ7.23ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ
13
2H),ꢀ7.44ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl ,ꢀ100ꢀMHz)ꢀδꢀ21.3ꢀ
3
(
CH
3
2
2
-
1
1
ν
ꢀ1327,ꢀ1587;ꢀ
+
HRMSꢀ(ESI/TOF)ꢀCalcdꢀforꢀC12
foundꢀ314.0333.ꢀꢀꢀ
H
15Cl
2
NO
3
Naꢀ[(M+Na) ]:ꢀ314.0321,ꢀ
(CH
129.1ꢀ(C),ꢀ129.5ꢀ(CH),ꢀ132.7ꢀ(CH),ꢀ140.1ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀ
3 2
),ꢀ70.8ꢀ(CH ),ꢀ84.8ꢀ(CH),ꢀ114.9ꢀ(C),ꢀ118.7ꢀ(CH2),ꢀ129.0ꢀ(CH),ꢀ
-
1
ν
ꢀ
1
-[2,2-dichloro-1-(4-methoxybenzyloxy)-2-nitroethyl]-4-
1339,ꢀ 1587;ꢀ HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ C12
H
13Cl
2
NO
3
Naꢀ
+
[(M+Na) ]:ꢀ312.0165,ꢀfoundꢀ312.0176.ꢀꢀ
methylbenzeneꢀ(3r).ꢀColorlessꢀoilꢀ(93.8ꢀmg,ꢀ0.25ꢀmmol,ꢀ83%).ꢀ
1
HꢀNMRꢀ(CDCl3,ꢀ400ꢀMHz)ꢀδꢀ2.41ꢀ(s,ꢀ3H),ꢀ3.80ꢀ(s,ꢀ3H),ꢀ4.25ꢀ(d,ꢀJꢀ
1-[2,2-Dichloro-2-nitro-1-(prop-2-ynyloxy)ethyl]-4-methylꢀ
1
benzeneꢀ(3y).ꢀColorlessꢀoilꢀ(39.0ꢀmg,ꢀ0.14ꢀmmol,ꢀ45%).ꢀ HꢀNMRꢀ
=
=
7
5
ꢀ11.2ꢀHz,ꢀ1H),ꢀ4.50ꢀ(d,ꢀJꢀ=ꢀ11.2ꢀHz,ꢀ1H),ꢀ5.28ꢀ(s,ꢀ1H),ꢀ6.85ꢀ(d,ꢀJꢀ
ꢀ8.0ꢀHz,ꢀ2H),ꢀ7.08ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H),ꢀ7.25ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H),ꢀ
(CDCl
3
,ꢀ400ꢀMHz)ꢀδꢀ2.40ꢀ(s,ꢀ3H),ꢀ2.47ꢀ(dd,ꢀJꢀ=ꢀ2.4,ꢀ2.4ꢀHz,ꢀ1H),ꢀ
1
.45ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
3
3 3
,ꢀ100ꢀMHz)ꢀδꢀ21.3ꢀ(CH ),ꢀ
3.96ꢀ(dd,ꢀJꢀ=ꢀ2.4,ꢀ16.0ꢀHz,ꢀ1H),ꢀ4.25ꢀ(dd,ꢀJꢀ=ꢀ2.4,ꢀ16.0ꢀHz,ꢀ1H),ꢀ
1
3
5.3ꢀ(CH ),ꢀ71.4ꢀ(CH ),ꢀ84.5ꢀ(CH),ꢀ113.9ꢀ(CH),ꢀ115.0ꢀ(C),ꢀ127.9ꢀ
3
2
5.57ꢀ(s,ꢀ1H),ꢀ7.24ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H),ꢀ7.45ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H);ꢀ Cꢀ
NMRꢀ(CDCl ,ꢀ100ꢀMHz)ꢀδꢀ21.3ꢀ(CH ),ꢀ56.8ꢀ(CH ),ꢀ76.4ꢀ(CH),ꢀ77.1ꢀ
(C),ꢀ 84.1ꢀ (CH),ꢀ 114.7ꢀ (C),ꢀ 128.0ꢀ (C),ꢀ 129.2ꢀ (CH),ꢀ 129.7ꢀ (CH),ꢀ
(
C),ꢀ129.0ꢀ(C),ꢀ129.1ꢀ(CH),ꢀ129.7ꢀ(CH),ꢀ129.9ꢀ(CH),ꢀ140.1ꢀ(C),ꢀ
3
3
2
-
1
1
59.7ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀ
NO Naꢀ[(M+Na) ]:ꢀ392.0427,ꢀfoundꢀ392.0442.ꢀꢀ
-[(2,2-Dichloro-2-nitro-1-(2-phenylethoxy)ethyl]-4-methylꢀ
νꢀ1325,ꢀ1587;ꢀHRMSꢀ(ESI/TOF)ꢀCalcdꢀ
+
-1
forꢀC17
H
17Cl
2
4
140.4ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀ
ν
ꢀ1333,ꢀ1589,ꢀ2124;ꢀHRMSꢀ(ESI/TOF)ꢀ
+
Naꢀ [(M+Na) ]:ꢀ 310.0008,ꢀ foundꢀ
1
Calcdꢀ forꢀ C12
310.0018.ꢀꢀ
H
11Cl
2
NO
3
1
benzeneꢀ(3s).ꢀColorlessꢀoilꢀ(52.6ꢀmg,ꢀ0.15ꢀmmol,ꢀ49%).ꢀ HꢀNMRꢀ
CDCl ,ꢀ400ꢀMHz)ꢀδꢀ2.36ꢀ(s,ꢀ3H),ꢀ2.81ꢀ(dd,ꢀJꢀ=ꢀ6.8,ꢀ6.8ꢀHz,ꢀ2H),ꢀ
.53–3.63ꢀ(m,ꢀ2H),ꢀ5.27ꢀ(s,ꢀ1H),ꢀ7.11ꢀ(d,ꢀJꢀ=ꢀ6.8ꢀHz,ꢀ2H),ꢀ7.16ꢀ(d,ꢀ
(
3
1-(2,2-Dibromo-1-methoxy-2-nitroethyl)-4-methylbenzeneꢀ
1
(4a).ꢀColorlessꢀoilꢀ(91.1ꢀmg,ꢀ0.26ꢀmmol,ꢀ85%).ꢀ HꢀNMRꢀ(CDCl
3
3
,ꢀ
1
3
Jꢀ=ꢀ8.0ꢀHz,ꢀ2H),ꢀ7.20–7.27ꢀ(m,ꢀ3H),ꢀ7.30ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H);ꢀ Cꢀ
NMRꢀ(CDCl ,ꢀ100ꢀMHz)ꢀδꢀ21.3ꢀ(CH ),ꢀ36.0ꢀ(CH ),ꢀ71.2ꢀ(CH ),ꢀ86.1ꢀ
CH),ꢀ114.7ꢀ(C),ꢀ126.4ꢀ(CH),ꢀ128.3ꢀ(CH),ꢀ128.9ꢀ(CH),ꢀ129.0ꢀ(CH),ꢀ
400ꢀMHz)ꢀδꢀ2.40ꢀ(s,ꢀ3H),ꢀ3.31ꢀ(s,ꢀ3H),ꢀ5.13ꢀ(s,ꢀ1H),ꢀ7.23ꢀ(d,ꢀJꢀ=ꢀ
1
3
3
3
2
2
8.0ꢀHz,ꢀ2H),ꢀ7.50ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
δꢀ21.3ꢀ(CH ),ꢀ57.9ꢀ(CH ),ꢀ88.1ꢀ(CH),ꢀ93.3ꢀ(C),ꢀ128.9ꢀ(CH),ꢀ129.4ꢀ
(C),ꢀ129.8ꢀ(CH),ꢀ140.0ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀ
3
,ꢀ100ꢀMHz)ꢀ
(
3
3
-
1
-1
1
1
3
1
29.2ꢀ(C),ꢀ129.4ꢀ(CH),ꢀ138.0ꢀ(C),ꢀ140.0ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀ
NO
ν
ꢀ1328,ꢀ
νꢀ1329,ꢀ1576;ꢀHRMSꢀ
+
Naꢀ [(M+Na) ]:ꢀ
+
587;ꢀ HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ C17
76.0478,ꢀfoundꢀ376.0493.ꢀꢀ
H
17Cl
2
3
(ESI/TOF)ꢀ Calcdꢀ forꢀ C10
foundꢀ373.9016.ꢀꢀꢀꢀ
2 3
H11Br NO Naꢀ [(M+Na) ]:ꢀ 373.8998,ꢀ
-[2,2-Dichloro-1-(3-methylbutoxy)-2-nitroethyl]-4-methylꢀ
1-(2-Iodo-1-methoxy-2-nitroethyl)-4-methylbenzeneꢀ(6a).ꢀ
Colorlessꢀ oilꢀ (33.8ꢀ mg,ꢀ 0.11ꢀ mmol,ꢀ 35%).ꢀ Aꢀ pairꢀ ofꢀ
1
diastereoisomersꢀwereꢀdetectedꢀwithꢀaꢀratioꢀofꢀ76/24.ꢀ HꢀNMRꢀ
1
benzeneꢀ(3t).ꢀColorlessꢀoilꢀ(43.7ꢀmg,ꢀ0.14ꢀmmol,ꢀ45%).ꢀ HꢀNMRꢀ
CDCl ,ꢀ400ꢀMHz)ꢀδꢀ0.82ꢀ(d,ꢀJꢀ=ꢀ6.8ꢀHz,ꢀ3H),ꢀ0.84ꢀ(d,ꢀJꢀ=ꢀ6.8ꢀHz,ꢀ
H),ꢀ1.33–1.47ꢀ(m,ꢀ2H),ꢀ1.58–1.68ꢀ(m,ꢀ1H),ꢀ2.39ꢀ(s,ꢀ3H),ꢀ3.32–
.38ꢀ(m,ꢀ1H),ꢀ3.43–3.48ꢀ(m,ꢀ1H),ꢀ5.24ꢀ(s,ꢀ1H),ꢀ7.25ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ
(
3
3
3
2
(CDCl
3H),ꢀ4.82ꢀ(d,ꢀJꢀ=ꢀ10.0ꢀHz,ꢀ1H),ꢀ6.17ꢀ(d,ꢀJꢀ=ꢀ10.0ꢀHz,ꢀ1H),ꢀ7.22ꢀ(d,ꢀ
3
,ꢀ400ꢀMHz)ꢀofꢀtheꢀmajorꢀisomer:ꢀδꢀ2.39ꢀ(s,ꢀ3H),ꢀ3.22ꢀ(s,ꢀ
1
3
13
H),ꢀ7.44ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
),ꢀ22.3ꢀ(CH ),ꢀ22.5ꢀ(CH ),ꢀ24.7ꢀ(CH),ꢀ38.1ꢀ(CH
6.1ꢀ(CH),ꢀ114.9ꢀ(C),ꢀ128.9ꢀ(CH),ꢀ129.4ꢀ(CH),ꢀ129.6ꢀ(C),ꢀ139.9ꢀ
3
,ꢀ100ꢀMHz)ꢀδꢀ21.3ꢀ
Jꢀ=ꢀ8.0ꢀHz,ꢀ2H),ꢀ7.26ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
MHz)ꢀδꢀ21.3ꢀ(CH ),ꢀ57.3ꢀ(CH),ꢀ57.9ꢀ(CH ),ꢀ86.0ꢀ(CH),ꢀ128.3ꢀ(CH),ꢀ
129.5ꢀ(CH),ꢀ131.2ꢀ(C),ꢀ139.8ꢀ(C).ꢀ HꢀNMRꢀ(CDCl ,ꢀ400ꢀMHz)ꢀofꢀ
3
,ꢀ100ꢀ
(
CH
3
3
3
2
),ꢀ69.1ꢀ(CH ),ꢀ
2
3
3
1
8
3
-
1
(
C);ꢀ IRꢀ (ATR/cm )ꢀ
NO
ν
ꢀ 1326,ꢀ 1588;ꢀ HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ
+
3
Naꢀ[(M+Na) ]:ꢀ342.0634,ꢀfoundꢀ342.0646.ꢀꢀ
theꢀminorꢀisomer:ꢀδꢀ2.24ꢀ(s,ꢀ3H),ꢀ3.33ꢀ(s,ꢀ3H),ꢀ4.57ꢀ(d,ꢀJꢀ=ꢀ7.6ꢀHz,ꢀ
1H),ꢀ6.24ꢀ(d,ꢀJꢀ=ꢀ7.6ꢀHz,ꢀ1H),ꢀ7.18ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H),ꢀ7.22ꢀ(d,ꢀJꢀ=ꢀ
C
14
H
19Cl
2
1
3
1
-(2,2-Dichloro-1-isopropoxy-2-nitroethyl)-4-methylbenzeneꢀ
,ꢀ
00ꢀMHz)ꢀδꢀ1.04ꢀ(d,ꢀJꢀ=ꢀ6.4ꢀHz,ꢀ3H),ꢀ1.09ꢀ(d,ꢀJꢀ=ꢀ6.4ꢀHz,ꢀ3H),ꢀ2.39ꢀ
8.0ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
60.0ꢀ(CH ),ꢀ84.1ꢀ(CH),ꢀ127.4ꢀ(CH),ꢀ129.7ꢀ(CH),ꢀ131.2ꢀ(C),ꢀ139.8ꢀ
(C);ꢀ IRꢀ (ATR/cm )ꢀ
Naꢀ[(M+Na) ]:ꢀ343.9754,ꢀfoundꢀ343.9756.ꢀꢀꢀꢀꢀ
1-(1-Methoxy-2-nitroethyl)-4-methylbenzeneꢀ (7a).ꢀ Colorlessꢀ
3 3
,ꢀ100ꢀMHz)ꢀδꢀ21.2ꢀ(CH ),ꢀ57.5ꢀ(CH),ꢀ
1
3u).ꢀColorlessꢀoilꢀ(37.6ꢀmg,ꢀ0.13ꢀmmol,ꢀ42%).ꢀ HꢀNMRꢀ(CDCl
(
3
3
-
1
4
νꢀ 1351,ꢀ 1559;ꢀ HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ
+
(
s,ꢀ3H),ꢀ3.60ꢀ(qq,ꢀJꢀ=ꢀ6.4,ꢀ6.4ꢀHz,ꢀ1H),ꢀ5.33ꢀ(s,ꢀ1H),ꢀ7.21ꢀ(d,ꢀJꢀ=ꢀ
10 3
C H12INO
1
3
8
.0ꢀHz,ꢀ2H),ꢀ7.45ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
),ꢀ21.2ꢀ(CH ),ꢀ22.9ꢀ(CH ),ꢀ72.5ꢀ(CH),ꢀ84.1ꢀ(CH),ꢀ115.4ꢀ
C),ꢀ128.8ꢀ(CH),ꢀ129.4ꢀ(CH),ꢀ130.6ꢀ(C),ꢀ139.8ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀ
3
,ꢀ100ꢀMHz)ꢀ
1
δꢀ20.8ꢀ(CH
3
3
3
oilꢀ(9.0ꢀmg,ꢀ0.05ꢀmmol,ꢀ15%).ꢀ HꢀNMRꢀ(CDCl
3
,ꢀ400ꢀMHz)ꢀδꢀ2.37ꢀ
-
1
(
(s,ꢀ3H),ꢀ3.26ꢀ(s,ꢀ3H),ꢀ4.37ꢀ(dd,ꢀJꢀ=ꢀ3.2,ꢀ12.8ꢀHz,ꢀ1H),ꢀ4.60ꢀ(dd,ꢀJꢀ=ꢀ
1
0.0,ꢀ12.8ꢀHz,ꢀ1H),ꢀ4.91ꢀ(dd,ꢀJꢀ=ꢀ3.2,ꢀ10.0ꢀHz,ꢀ1H),ꢀ7.21ꢀ(d,ꢀJꢀ=ꢀ
6
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Page 7 of 8
O rP gl ea na si ce &ꢀ d Bo i ꢀon mo to ꢀ al e dc juu l sa tr ꢀ mC haer mg i ins ts rꢀ y
JournalꢀNameꢀ
ꢀARTICLEꢀ
1
3
3
4
J.ꢀLi,ꢀM.ꢀJ.ꢀLear,ꢀE.ꢀKwonꢀandꢀY.ꢀHayashi,ꢀChem.VꢀEieuwrA.rꢀtJi.c,lꢀe2O0n1lin6e,
,ꢀ5538.ꢀ
(a)ꢀP.ꢀButler,ꢀB.ꢀT.ꢀGolding,ꢀG.ꢀLaval,ꢀH.ꢀLoghmani-Khouzani,ꢀ
ꢀ
8
.4ꢀHz,ꢀ2H),ꢀ7.25ꢀ(d,ꢀJꢀ=ꢀ8.4ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
δꢀ21.2ꢀ(CH ),ꢀ57.0ꢀ(CH ),ꢀ79.9ꢀ(CH),ꢀ80.5ꢀ(CH ),ꢀ126.8ꢀ(CH),ꢀ129.7ꢀ
CH),ꢀ132.9ꢀ(C),ꢀ139.1ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀ ꢀ1330,ꢀ1559;ꢀHRMSꢀ
3
,ꢀ100ꢀMHz)ꢀ
2
2
DOI: 10.1039/C8OB00408K
3
3
2
-
1
(
(
ν
R.ꢀRanjbar-KarimiꢀandꢀM.ꢀM.ꢀSadeghi,ꢀTetrahedron,ꢀ2007,ꢀ63,ꢀ
+
3
ESI/TOF)ꢀCalcdꢀforꢀC10H13NO Naꢀ[(M+Na) ]:ꢀ218.0788,ꢀfoundꢀ
1
1160;ꢀ(b)ꢀA.ꢀI.ꢀIlovaisky,ꢀV.ꢀM.ꢀMerkulova,ꢀY.ꢀN.ꢀOgibinꢀandꢀ
2
18.0796.ꢀꢀ
-(2-Fluoro-1-methoxy-2-nitroethyl)-4-methylbenzeneꢀ (9a).ꢀ
G.ꢀI.ꢀNikishin,ꢀRuss.ꢀChem.ꢀBull.,ꢀInt.ꢀEd.,ꢀ2005,ꢀ54,ꢀ1585.ꢀꢀ
A.ꢀV.ꢀFokin,ꢀA.ꢀI.ꢀRapkinꢀandꢀV.ꢀA.ꢀKomarov,ꢀRuss.ꢀChem.ꢀBull.,ꢀ
1982,ꢀ31,ꢀ1585.ꢀ
S.ꢀJ.ꢀZhi,ꢀH.ꢀSun,ꢀC.ꢀLin,ꢀG.ꢀQ.ꢀZhang,ꢀG.ꢀG.ꢀLiꢀandꢀY.ꢀPan,ꢀSci.ꢀ
China,ꢀChem.,ꢀ2010,ꢀ53,ꢀ140.ꢀꢀ
S.ꢀJ.ꢀZhi,ꢀH.ꢀB.ꢀMei,ꢀG.ꢀQ.ꢀZhang,ꢀH.ꢀSun,ꢀJ.ꢀL.ꢀHan,ꢀG.ꢀG.ꢀLiꢀandꢀ
Y.ꢀPan,ꢀSci.ꢀChina,ꢀChem.,ꢀ2010,ꢀ53,ꢀ1946.ꢀꢀ
Z.ꢀG.ꢀChen,ꢀY.ꢀWang,ꢀJ.ꢀF.ꢀWei,ꢀP.ꢀF.ꢀZhaoꢀandꢀX.ꢀY.ꢀShi.ꢀJ.ꢀOrg.ꢀ
Chem.,ꢀ2010,ꢀ75,ꢀ2085.ꢀ
5
6
7
8
9
1
1
1
Colorlessꢀoilꢀ(11.1ꢀmg,ꢀ0.05ꢀmmol,ꢀ17%).ꢀ HꢀNMRꢀ(CDCl
3
,ꢀ400ꢀ
MHz)ꢀδꢀ2.38ꢀ(s,ꢀ3H),ꢀ3.31ꢀ(s,ꢀ3H),ꢀ4.68ꢀ(dd,ꢀJꢀ=ꢀ5.6,ꢀ13.6ꢀHz,ꢀ1H),ꢀ
1
3
5
.84ꢀ(dd,ꢀJꢀ=ꢀ5.6,ꢀ50.0ꢀHz,ꢀ1H),ꢀ7.23–7.24ꢀ(d,ꢀ4H,ꢀoverlap);ꢀ Cꢀ
NMRꢀ(CDCl ,ꢀ100ꢀMHz)ꢀδꢀ21.3ꢀ(CH ),ꢀ57.4ꢀ(CH ),ꢀ81.6ꢀ(d,ꢀJꢀ=ꢀ22.8ꢀ
Hz,ꢀCH),ꢀ111.1ꢀ(d,ꢀJꢀ=ꢀ238.9ꢀHz,ꢀCH),ꢀ127.8ꢀ(CH),ꢀ129.5ꢀ(C),ꢀ129.7ꢀ
3
3
3
-
1
(
CH),ꢀ139.9ꢀ(C);ꢀIRꢀ(ATR/cm )ꢀνꢀ1346,ꢀ1515;ꢀHRMSꢀ(ESI/TOF)ꢀ
+
S.ꢀJ.ꢀZhi,ꢀJ.ꢀL.ꢀHan,ꢀC.ꢀLin,ꢀG.ꢀH.ꢀAn,ꢀY.ꢀPanꢀandꢀG.ꢀG.ꢀLi,ꢀSynthesis,ꢀ
CalcdꢀforꢀC10
3
H12FNO Naꢀ[(M+Na) ]:ꢀ236.0693,ꢀfoundꢀ236.0704.ꢀꢀ
2
008,ꢀ1570.ꢀꢀꢀ
Allylationꢀofꢀ3aꢀ
0 (a)ꢀS.ꢀS.ꢀR.ꢀS.ꢀKotti,ꢀC.ꢀTimmonsꢀandꢀG.ꢀLi,ꢀChem.ꢀBiol.ꢀDrug.ꢀ
Des.,ꢀ2006,ꢀ67,ꢀ101;ꢀ(b)ꢀD.ꢀLucet,ꢀL.ꢀToupet,ꢀT.ꢀL.ꢀGallꢀandꢀC.ꢀ
Mioskowski,ꢀJ.ꢀOrg.ꢀChem.,ꢀ1997,ꢀ62,ꢀ2682;ꢀ(c)ꢀD.ꢀEndersꢀandꢀ
J.ꢀWiedemann,ꢀSynthesis,ꢀ1996,ꢀ1443.ꢀ
Toꢀaꢀsolutionꢀofꢀ3aꢀ(51.9ꢀmg,ꢀ0.20ꢀmmol)ꢀinꢀtolueneꢀ(1.6ꢀmL),ꢀ
wereꢀ addedꢀ allyltributyltinꢀ (151.2ꢀ ,ꢀ 0.49ꢀ mmol)ꢀ andꢀ
µ
L
azobis(isobutyronitrile)ꢀ(0.1ꢀmmol,ꢀ15.6ꢀmg)ꢀsuccessively.ꢀTheꢀ
resultantꢀ mixtureꢀ wasꢀ heatedꢀ atꢀ 120ꢀ ℃ꢀ forꢀ 9ꢀ h.ꢀ Then,ꢀ theꢀ
solventꢀ wasꢀ evaporatedꢀ toꢀ affordꢀ aꢀ reactionꢀ mixtureꢀ asꢀ aꢀ
yellowꢀoil,ꢀwhichꢀwasꢀtreatedꢀbyꢀcolumnꢀchromatographyꢀonꢀ
1
1
1 F.ꢀ Hao,ꢀ H.ꢀ Asaharaꢀ andꢀ N.ꢀ Nishiwaki,ꢀ Org.ꢀ Biomol.ꢀ Chem.,ꢀ
2016,ꢀ14,ꢀ5128.ꢀ
2 (a)ꢀU.ꢀJahn,ꢀD.ꢀRudakovꢀandꢀP.ꢀG.ꢀJones,ꢀTetrahedron,ꢀ2012,ꢀ
68,ꢀ 1521;ꢀ (b)ꢀ E.ꢀ Dumez,ꢀ A.ꢀ C.ꢀ Durand,ꢀ M.ꢀ Guillaume,ꢀ P.ꢀ Y.ꢀ
Roger,ꢀ R.ꢀ Faure,ꢀ J.ꢀ M.ꢀ Pons,ꢀ G.ꢀ Herbette,ꢀ J.ꢀ P.ꢀ Dulcère,ꢀ D.ꢀ
silicaꢀgelꢀtoꢀaffordꢀ14ꢀ(elutedꢀwithꢀEt
2
O/hexaneꢀ=ꢀ1/120,ꢀ29.1ꢀ
BonneꢀandꢀJ.ꢀRodriguez,ꢀChem.ꢀEur.ꢀJ.,ꢀ2009,ꢀ15,ꢀ12470.ꢀ
3 Regardingꢀ a,β-unsaturatedꢀ carbonylꢀ compounds,ꢀ someꢀ
1
mg,ꢀ0.11ꢀmmol,ꢀ55%ꢀyield)ꢀasꢀaꢀcolorlessꢀoil.ꢀ HꢀNMRꢀ(CDCl
3
,ꢀ
00ꢀMHz)ꢀδꢀ2.29ꢀ(s,ꢀ3H),ꢀ2.89ꢀ(dddd,ꢀJꢀ=ꢀ1.2,ꢀ1.2,ꢀ6.4,ꢀ14.4ꢀHz,ꢀ
H),ꢀ2.99ꢀ(dddd,ꢀJꢀ=ꢀ1.2,ꢀ1.2,ꢀ7.2,ꢀ14.4ꢀHz,ꢀ1H),ꢀ3.22ꢀ(s,ꢀ3H),ꢀ4.35ꢀ
1
4
1
reportsꢀforꢀtheꢀalkoxy-dihalogenationꢀareꢀfound,ꢀhowever,ꢀ
theꢀ activationꢀ ofꢀ theꢀ doubleꢀ bondꢀ byꢀ aꢀ heteroꢀ atomꢀ isꢀ
required.ꢀ Chlorinationꢀ byꢀ chlorineꢀ molecule:ꢀ (a)ꢀ V.ꢀ G.ꢀ
Kasrazdze,ꢀ I.ꢀ B.ꢀ Ignatyeva,ꢀ R.ꢀ A.ꢀ Khusnutdinov,ꢀ K.ꢀ Y.ꢀ
Suponitskii,ꢀ M.ꢀ Y.ꢀ Antipinꢀ andꢀ M.ꢀ S.ꢀ Yunusov,ꢀ Chem.ꢀ
Heterocycl.ꢀCompd.,ꢀ2012,ꢀ48,ꢀ1018;ꢀ(b)ꢀV.ꢀJakubkieneꢀandꢀP.ꢀ
Vainilavicius,ꢀChem.ꢀHeterocycl.ꢀCompd.,ꢀ2006,ꢀ42,ꢀ788;ꢀ(c)ꢀꢀF.ꢀ
I.ꢀGuseinovꢀandꢀV.ꢀV.ꢀMoskva,ꢀZh.ꢀOrg.ꢀKhim.ꢀ1994,ꢀ30,ꢀ360.ꢀ
Chlorinationꢀ byꢀ sodiumꢀ dichlorocyanurate:ꢀ (d)ꢀ B.ꢀ Staskunꢀ
andꢀT.ꢀVanꢀEs,ꢀJ.ꢀChem.ꢀSoc.,ꢀPerkinꢀTrans.ꢀ1,ꢀ1993,ꢀ511.ꢀ
4 (a)ꢀR.ꢀDingꢀandꢀC.ꢀWolf,ꢀChem.ꢀCommun.,ꢀ2016,ꢀ52,ꢀ3576;ꢀ(b)ꢀ
R.ꢀBallini,ꢀM.ꢀPetriniꢀandꢀO.ꢀPolimanti,ꢀJ.ꢀOrg.ꢀChem.,ꢀ1996,ꢀ
(
s,ꢀ1H),ꢀ5.16ꢀ(dddd,ꢀJꢀ=ꢀ1.2,ꢀ1.2,ꢀ2.8,ꢀ16.8ꢀHz,ꢀ1H),ꢀ5.20ꢀ(dddd,ꢀJꢀ
ꢀ1.2,ꢀ1.2,ꢀ2.8,ꢀ10.4ꢀHz,ꢀ1H),ꢀ5.90–6.00ꢀ(m,ꢀ1H),ꢀ7.11ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀ
=
1
3
Hz,ꢀ2H),ꢀ7.30ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H);ꢀ CꢀNMRꢀ(CDCl
1.3ꢀ(CH ),ꢀ48.2ꢀ(CH ),ꢀ57.6ꢀ(CH ),ꢀ89.0ꢀ(CH),ꢀ93.2ꢀ(C),ꢀ120.4ꢀ
CH ),ꢀ128.5ꢀ(CH),ꢀ129.7ꢀ(CH),ꢀ131.7ꢀ(CH),ꢀ132.0ꢀ(C),ꢀ138.7ꢀ(C);ꢀ
IRꢀ (ATR/cm )ꢀ
16ClNO Naꢀ[(M+Na) ]:ꢀ292.0711,ꢀfoundꢀ292.0724.ꢀꢀ
3
,ꢀ100ꢀMHz)ꢀδꢀ
2
3
2
3
(
2
-
1
ν
ꢀ 1346,ꢀ 1565;ꢀ HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ
+
C
13
H
3
1
Eliminationꢀofꢀnitrousꢀacidꢀfromꢀ3aꢀꢀ
61,ꢀ5652.ꢀ
Toꢀaꢀsolutionꢀofꢀ3aꢀ(36.1ꢀmg,ꢀ0.14ꢀmmol)ꢀinꢀMeOHꢀ(1.0ꢀmL),ꢀ
wasꢀ addedꢀ MeONaꢀ (0.69ꢀ mmol,ꢀ 37.0ꢀ mg).ꢀ Theꢀ resultantꢀ
mixtureꢀwasꢀheatedꢀatꢀ70ꢀ℃ꢀforꢀ22ꢀh.ꢀThen,ꢀtheꢀsolventꢀwasꢀ
evaporatedꢀtoꢀaffordꢀaꢀreactionꢀmixtureꢀasꢀaꢀyellowꢀoil,ꢀwhichꢀ
wasꢀtreatedꢀbyꢀcolumnꢀchromatographyꢀonꢀsilicaꢀgelꢀtoꢀaffordꢀ
1
1
5 E.ꢀR.ꢀJohnson,ꢀW.ꢀT.ꢀReed,ꢀC.ꢀH.ꢀTiemanꢀandꢀS.ꢀB.ꢀSoloway,ꢀUSꢀ
Pat.,ꢀUS3830921,ꢀ1974.ꢀꢀ
6 Y.ꢀG.ꢀBal’on,ꢀM.ꢀD.ꢀShul’manꢀandꢀV.ꢀE.ꢀParanyuk,ꢀUkr.ꢀKhim.ꢀ
Zh.,ꢀ1990,ꢀ56,ꢀ83.ꢀ
7 J.ꢀT.ꢀLiuꢀandꢀC.ꢀF.ꢀYao,ꢀTetrahedronꢀLett.,ꢀ2001,ꢀ42,ꢀ6147.ꢀ
8 (a)ꢀ K.ꢀ Kiyokawa,ꢀ T.ꢀ Nagata,ꢀ J.ꢀ Hayakawaꢀ andꢀ S.ꢀ Minakata,ꢀ
Chem.ꢀEur.ꢀJ.,ꢀ2015,ꢀ21,ꢀ1280;ꢀ(b)ꢀA.ꢀJ.ꢀSimpsonꢀandꢀH.ꢀW.ꢀLam,ꢀ
Org.ꢀLett.,ꢀ2013,ꢀ15,ꢀ2586.ꢀꢀ
1
1
1
5
ꢀ (elutedꢀ withꢀ CH
2 2
Cl /hexaneꢀ =ꢀ 1/6,ꢀ 29.6ꢀ mg,ꢀ 0.14ꢀ mmol,ꢀ
1
quant.)ꢀasꢀaꢀcolorlessꢀoil.ꢀ HꢀNMRꢀ(CDCl
3
3
,ꢀ400ꢀMHz)ꢀδꢀ2.39ꢀ(s,ꢀ
H),ꢀ3.45ꢀ(s,ꢀ3H),ꢀ7.23ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H),ꢀ7.36ꢀ(d,ꢀJꢀ=ꢀ8.0ꢀHz,ꢀ2H);ꢀ
1
3
CꢀNMRꢀ(CDCl
3 3 3
,ꢀ100ꢀMHz)ꢀδꢀ21.4ꢀ(CH ),ꢀ58.1ꢀ(CH ),ꢀ108.5ꢀ(C),ꢀ
1
28.5ꢀ (C),ꢀ 129.1ꢀ (CH),ꢀ 129.2ꢀ (CH),ꢀ 139.6ꢀ (C),ꢀ 152.2ꢀ (C);ꢀ IRꢀ
-
ATR/cm )ꢀ
1
(
[
ν
(M+H) ]:ꢀ217.0182,ꢀfoundꢀ217.0190.ꢀꢀ
ꢀ 1610;ꢀ HRMSꢀ (ESI/TOF)ꢀ Calcdꢀ forꢀ C10
2
H11Cl Oꢀ
+
Notesꢀandꢀreferencesꢀ
1
2
ꢀ(a)ꢀV.ꢀA.ꢀZapol’skii,ꢀJ.ꢀC.ꢀNamyslo,ꢀG.ꢀSergeev,ꢀM.ꢀBrönstrup,ꢀ
M.ꢀGjikajꢀandꢀD.ꢀE.ꢀKaufmann,ꢀEur.ꢀJ.ꢀOrg.ꢀChem.,ꢀ2015,ꢀ7763;ꢀ
(
b)ꢀL.ꢀQian,ꢀY.ꢀShen,ꢀJ.ꢀChenꢀandꢀK.ꢀZheng,ꢀActaꢀPhys.ꢀ-Chim.ꢀ
Sin.,ꢀ2006,ꢀ22,ꢀ1372;ꢀ(c)ꢀM.ꢀDavidꢀandꢀP.ꢀBipin,ꢀPCTꢀInt.ꢀAppl.,ꢀ
WO9422851,ꢀ1994;ꢀ(d)ꢀA.ꢀL.ꢀFridman,ꢀV.ꢀS.ꢀZalesov,ꢀV.ꢀSurkov,ꢀ
L.ꢀV.ꢀKratynskayaꢀandꢀA.ꢀN.ꢀPlaksina,ꢀPharm.ꢀChem.ꢀJ.,ꢀ1976,ꢀ
10,ꢀ53;ꢀ(e)ꢀN.ꢀG.ꢀClark,ꢀB.ꢀCroshaw,ꢀB.ꢀE.ꢀLeggetterꢀandꢀD.ꢀF.ꢀ
Spooner,ꢀJ.ꢀMed.ꢀChem.,ꢀ1974,ꢀ17,ꢀ977.ꢀꢀ
R.ꢀDing,ꢀP.ꢀR.ꢀBakhshiꢀandꢀC.ꢀWolf,ꢀJ.ꢀOrg.ꢀChem.,ꢀ2017,ꢀ82,ꢀ
1
273.ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ7ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Organic & Biomolecular Chemistry
Page 8 of 8
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DOI: 10.1039/C8OB00408K
O
1
NO2
R O
NO2
X
NaH
1
+
R OH
+
N X
2
6 examples
up to 90%
R
R
X
O
X = Br, Cl
A direct alkoxy-dihalogenation method of nitroalkenes was developed by
three component reaction using alcohol and -halosuccinimide.
N