RESEARCH PAPER JUNE± -2851$/2)&+(0,&$/5(6($5&+

Electrophilic aromatic substitution of 7-t-butyl-1,3-dimethylpyrene:

preparation of 5-mono- and 5,9-di-substituted
7-t-butyl-1,3-dimethylpyrenes
Jian-yong Hu, Arjun Paudel and Takehiko Yamato*
Department of Applied Chemistry, Faculty of Science and Engineering, Saga University, Honjo-machi 1, Saga-shi, Saga 840-8502,
Japan

Formylation and acetylation of 7-t-butyl-1,3-dimethylpyrene selectively afforded the 5-mono- and 5,9-di-substitution
products depending on the Lewis acid catalyst used, while bromination and nitration afforded the 6-substitution
product.

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mutations in living organisms,1 thus making them the largest
class of chemical carcinogens today. Pyrenes are formed
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Reference materials are essential also for the study of the
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of 2 ZLWK HTXLPRODU %70$ %U3 under the same conditions
DERYH DIIRUGHG GLEURPRS\UHQH 3) in quantitative yield.
On the other hand, when nitration of 1 with copper(II)
nitrate trihydrate in acetic anhydride was carried out at room
temperature, the 6-nitro derivative 4 ZDV REWDLQHG LQ 
ELRORJLFDOHIIHFWVRISRO\F\FOLFDURPDWLFFRPSRXQGVDQGIRU \LHOG 6FKHPH  7KH nitronium ion attacks on the pyrene
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acetylation.±
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the formylation of 7-tEXW\OGLPHWK\OS\UHQH 1) with
dichloromethyl methyl ether in the presence of titanium
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GLUHFWHOHFWURSKLOLFVXEVWLWXWLRQRIS\UHQHLWVHOI of dichloromethyl methyl ether in methylene dichloride
:H SUHYLRXVO\ UHSRUWHG WKH FRQYHQLHQW SUHSDUDWLYH URXWH solution in the presence of AlCl3 afforded regioselectively
for 7-tEXW\OGLPHWK\OS\UHQH 1 IURP S\UHQH LQ  VWHSV
which involves formylation of 7-tEXW\OPHWK\OS\UHQH DQG
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WKHSUHVHQFHRI7L&O4 or AlCl3DVDFDWDO\VWWRDIIRUGDFHW\O
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Results and discussion (AlH2&OUHGXFWLRQVHHUHIDQGUHIVFLWHGWKHUHLQ)XUWKHU
formylation of 7 carried out with dichloromethyl methyl ether
7KH SUHSDUDWLRQ RI tEXW\OGLPHWK\OS\UHQH 1) was LQWKHSUHVHQFHRI7L&O4 afforded the 9-formyl derivative 8 in
carried out according to the reported procedure.12,13  \LHOG IURP ZKLFK tEXW\OWHWUDPHWK\OS\UHQH
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%70$%U3)14DIIRUGHGEURPRtEXW\OGLPHWK\OS\UHQH (Scheme 3). 7-t%XW\OWHWUDPHWK\OS\UHQH 9) was also
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EXW\OGLPHWK\OS\UHQH37KHUHODWLYHO\IDFLOHHOHFWURSKLOLF Consequently, we have succeeded in preparing a series of
VXEVWLWXWLRQ ortho to a tEXW\O JURXS SRVLWLRQ LQVWHDG PHWK\O VXEVWLWXWHG S\UHQH GHULYDWLYHV 7KH 89 VSHFWUD RI
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along with those of pyrene and 1-methyl-7-tEXW\OS\UHQH

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PAPER: 08/5074
 -2851$/2)&+(0,&$/5(6($5&+ 

Me Me Me Me
1 3 3 1
BTMA Br3
(1 equiv,)
+ 5
in CH2Cl2 Br
r.t. for 2 h 6 8
Me Me Br Br
(85%) 7

5
2 3
9

8 6 Me Me
Cu(NO3)2 3H2O
/Ac2O
1 r.t. for 1 h
(90%)
NO2

Scheme 1

Me Me Me Me
Cl2CHOMe 1 3

or MeCOCl
1 5 + 5
Lewis acid CR RC 9 CR
in CH2Cl2
O O O
7

5 a: R=H 6 a: R=H
b: R= Me b: R= Me

Scheme 2

Table 1 Formylation and acetylation of 7-t-butyl-1,3-dimethylpyrene (1)a

Run Reagents Lewis acids Reaction time/h Product yields/%b

5 6

1 Cl2CHOMe TiCl4 2 93 [69]c 0

2 Cl2CHOMe AlCl3 6 0 89 [80]
3 MeCOCl TiCl4 2 95 [85] c 0
4 MeCOCl AlCl3 3 0 100 [95]
aYields are determined by GLC analyses. bIsolated yields are shown in square parentheses. cThe starting compound 1 was
recovered in 7 and 5% yields, respectively.

Me Me Me Me
AlH2Cl Cl2CHOMe
5a
Et2O Me TiCl4 Me
OHC
reflux for 3 h in CH2Cl2
(86%) r.t. for 2 h
(90%)
7 8

Me Me
AlH2Cl
Et2O Me Me
reflux for 3 h
(85%)

9
Fig. 1 UV-vis absorption spectra of 1, 7, 9, 10 and pyrene in
dichloromethane in the range of 10– 5 –10 -6 M concentration at
Scheme 3 room temperature.

PAPER: 08/5074
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All melting points are uncorrected. 1H NMR spectra were recorded
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Preparation of 5-acetyl-7-t-butyl-1,3-dimethylpyrene (5b
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JHO:DNR&JZLWKKH[DQHDVDQHOXHQWWRDIIRUGFUXGH3 as (3 u  FP3), dried over Na2SO4, and concentrated under reduced
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PAPER: 08/5074
 -2851$/2)&+(0,&$/5(6($5&+ 

PJDV\HOORZSULVPVPS±ƒ&GH&'&O3 compound 9PJDVFRORXUOHVVSULVPVPS±ƒ&

(9H, s, t%X+VMe), 2.97 (6H, s, Me+V$UH2), GH &'&O3  + V t%X  + V Me), 2.92 (6H, s, Me),
+V$UH4,10), 9.17 (2H, s, ArH6,8); m/z0+). Anal. calcd. 7.64 (1H, s, ArH2+V$UH4,10), 8.31 (2H, s, ArH6,8); m/z
for C26H26O2&+)RXQG&+ 314 (M+). Anal. calcd. for C24H26&+)RXQG
Preparation of 7-t-butyl-1,3,5-trimethylpyrene (7 7R D VWLUUHG &+
solution of AlH2Cl [prepared from AlCl3  PJ  PPRO DQG
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solution of 7-tertEXW\OIRUP\OGLPHWK\OS\UHQH 5a) (314 mg, Similarly, compound 9ZDVSUHSDUHGE\WKHFKORURK\GURDODQH
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Received 30 January 2008; accepted 20 May 2008
Paper 08/5074 doi: 10.3184/030823408X324670
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5HFU\VWDOOLVDWLRQIURPKH[DQHWRDIIRUG7PJPS±   $ %M¡UVHWK DQG 7 5DPGDKO Handbook of polycyclic aromatic
126°C; GH&'&O3+Vt%X+VMe), 7.68 (1H, s, hydrocarbons HGV $ %M¡UVHWK DQG 7 5DPGDKO 0DUFHO 'HNNHU
ArH2+GJ +]$UH9+V$UH4), 8.17 (1H, 1HZ<RUNS
d, J +]$UH10), 8.21 (1H, d, J +]$UH8), 8.31 (1H, d, 2 E. Cavalieri and E. Rogan, Environ. Health Perspect.64, 69.
J +]$UH6); m/z0+). Anal. calcd. for C23H24 3 E. Clar, Polycyclic hydrocarbons $FDGHPLF 3UHVV 1HZ <RUN 
&+)RXQG&+ 9RO,,
Preparation of 7-t-butyl-9-formyl-1,3,5-trimethylpyrene (8   +9ROOPDQQ+%HFNHU0&RUUHODQG+6WUHHFNJustus Liebigs Ann.
)RUP\ODWLRQ RI 7  PJ  PPRO ZLWK GLFKORURPHWK\O PHWK\O Chem., 1937, 531, 1.
ether in the presence of titanium tetrachloride under the same reaction   $6WUHLWZLHVHU5*/DZOHUDQG'6FKZDDEJ. Org. Chem30,
conditions as preparation of 5aGHVFULEHGDERYHDIIRUGHGtEXW\O 147.
IRUP\OWULPHWK\OS\UHQH8 PJDVSDOH\HOORZSULVPV 6 M. Moyle and E. Ritchie, Aust. J. Chem.,11, 211.
PS ±ƒ& QPD[.%UFP-1        5*+DUYH\-3DWDNLDQG+/HHOrg. Prep. Proc. Int., 1984, 16, 144.
GH &'&O3  + V t%X  + V Me), 2.98 (3H, s, Me),   0 0LQDEH 6 7DNHVKLJH < 6RHGD 7 .LPXUD DQG 0 7VXERWD Bull.
2.98 (3H, s, Me+V$UH2), 7.98 (1H, s, ArH4), 8.39 (1H, Chem. Soc. Jpn., 1994, 67, 172.
  $0 %UDNHQYDQ /HHUVXP - &RUQHOLVVH DQG - /XJWHQEXUJ J. Chem.
d, J = +]$UH6), 8.67 (1H, s, ArH10), 9.78 (1H, d, J +]
Soc., Chem. Commun.
ArH8+V&HO); mz0+). Anal. calcd. for C24H24O
 5%ROWRQJ. Chem. Soc., 1964, 4637.
 &+)RXQG&+  30*%DYLQCan. J. Chem.37, 1614.
Preparation of 7-t-butyl-1,3,5,9-tetramethylpyrene (97RDVWLUUHG  7<DPDWR$0L\D]DZDDQG07DVKLURJ. Chem. Soc., Perkin Trans. 1,
solution of AlH2Cl [prepared from AlCl3  J  PPRO DQG 1993, 3127.
LiAlH4PJPPROLQGLHWK\OHWKHU@ZDVJUDGXDOO\DGGHGD  7<DPDWR and J. Hu, J. Chem. Res.
solution of 7-tEXW\OGLIRUP\OGLPHWK\OS\UHQH6a) (342 mg,  6.DMLJDHVKL7.DNLQDPL+7RNL\DPD7+LUDNDZDDQG72NDPRWR
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dried over Na2SO4, and the solvent evaporated under reduced
SUHVVXUH 7KH UHVLGXH ZDV FROXPQFKURPDWRJUDSKHG RYHU VLOLFD JHO
Chem. Lett., 1987, 627.
 *$2ODKAcc. Chem. Res., 1971, 4,
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 5%0RRGLHDQG.6FKR¿HOGAcc. Chem. Res., 1976, 9, 287.
 /) )LHVHU DQG 0 )LHVHU Reagents for Organic Synthesis :LOH\
1HZ<RUN9ROSS±
:DNR&JZLWKKH[DQHFKORURIRUPDVHOXHQWWRJLYH  . .DO\DQDVXQGDUDP DQG -. 7KRPDV J. Am. Chem. Soc., 1977, 99,
D FRORXUOHVV VROLG 5HFU\VWDOOLVDWLRQ IURP KH[DQH DIIRUGHG WKH title 

PAPER: 08/5074
 Journal of Chemical Research

2008 Issue No. 6

ISSN 0308-2342 JRPSDC
This journal is covered by the following secondary information sources: Chemical Abstracts, Current Contents,
Current Abstracts of Chemistry/Index Chemicus, Current Chemical Reactions, Current Bibliography on Science
and Technology, Science Citation Index, Bulletin Signalétique, Referativnyi Zhurnal and ChemInform

Contents
RESEARCH PAPERS

301 One-pot preparation of ternary and quaternary

iminium salts from aldehydes and ketones
R1 R3
N+ A

R2 R4
Shahrokh Saba, Diane Vrkic, Clair Cascella, Ida
DaSilva, Kristine Carta and Adeline Kojtari

305 Stereoselective synthesis of difunctionalised

1,3-dienes containing silicon and sulfur via
palladium catalysed cross-coupling reactions
Cp2TiCl2 (5 mol%) R SiMe3
R SiMe3 + i-BuMgBr
Et2O, 0~25°C H MgBr

Haiyun Zhang, Xinglin Ye and Mingzhong Cai

308 Electrophilic aromatic substitution of 7-t-butyl-

1,3-dimethylpyrene: preparation of 5-mono- and Me Me Me Me
5,9-di-substituted 7-t-butyl-1,3-dimethylpyrenes Cl2CHOMe
AlCl3 OHC CHO
in CH2Cl2
rt for 6 h
(80%)
Jian-yong Hu, Arjun Paudel and Takehiko Yamato

312 Alcohol substitution and dehydrogenation of

selenium compounds: a convenient preparation
R2 R1 R2 R1
of trisubstituted furans from allyl-substituted
(NH4)2S2O8
1,3-dicarbonyls
O O
O DMF, R3OH, 60 C
O O

SePh OR3

E Tang and Xian Huang

314 Microbiological hydroxylation of some epoxy

steroids by the fungus Mucor plumbeus O O

H Mucor plumbeus H
+ starting material
HO HO
O O
OH
Khalid. O. Alfooty