Synthesis of anthracene derivatives of 1,3-diazabicyclo[3.1.0]hex-3-ene

Article abstract of DOI:10.1016/j.molstruc.2014.10.019

Novel mono- and bis-photochromic compounds of 1,3-diazabicyclo[3.1.0]hex-3-enes based on anthracene moiety were synthesized efficiently. Photochromic compounds were synthesized through the reaction of 10-(hydroxymethyl)anthracene-9-carbaldehyde and anthracene-9-carbaldehyde or 9,10-anthracenedicarbaldehyde as bis-aldehydes with ketoaziridines in dry DMF at room temperature. Photochromic compounds exhibited photochromic behavior both in solution and in solid state by irradiation under UV light at 254 nm. Compounds bearing 4-NO₂ on aziridine moiety showed intensive color change. Compounds were characterized by IR, ¹H NMR, ¹³C NMR, and UV-Vis.

Full text of DOI:10.1016/j.molstruc.2014.10.019

Accepted Manuscript
Synthesis of Anthracene Derivatives of 1,3-Diazabicyclo[3.1.0]hex-3-ene
Nosrat O. Mahmoodi, Safoura Mirkhaef, Atefeh Ghavidast
PII:
S0022-2860(14)01021-7
DOI:
http://dx.doi.org/10.1016/j.molstruc.2014.10.019
MOLSTR 21015
Reference:
To appear in:
Journal of Molecular Structure
Received Date:
Revised Date:
Accepted Date:
18 August 2014
7 October 2014
9 October 2014
Please cite this article as: N.O. Mahmoodi, S. Mirkhaef, A. Ghavidast, Synthesis of Anthracene Derivatives of 1,3-
Diazabicyclo[3.1.0]hex-3-ene, Journal of Molecular Structure (2014), doi: http://dx.doi.org/10.1016/j.molstruc.
2
014.10.019
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Synthesis of Anthracene Derivatives of 1,3-Diazabicyclo[3.1.0]hex-3-ene
Nosrat O. Mahmoodi*, Safoura Mirkhaef, Atefeh Ghavidast
Chemistry Department, Faculty of Science, Guilan University, P. O. Box 41335-1914, Rasht, Iran
Corresponding Author. e-mail: mahmoodi@guilan.ac.ir
Abstract
Novel mono- and bis-photochromic compounds of 1,3-diazabicyclo[3.1.0]hex-3-enes based on anthracene
moiety were synthesized efficiently. Photochromic compounds were synthesized through the reaction of 10-
(
hydroxymethyl)anthracene-9-carbaldehyde and anthracene-9-carbaldehyde or 9,10-anthracenedicarbaldehyde
as bis-aldehydes with ketoaziridines in dry DMF at room temperature. Photochromic compounds exhibited
photochromic behavior both in solution and in solid state by irradiation under UV light at 254 nm. Compounds
1
bearing 4-NO
2
on aziridine moiety showed intensive color change. Compounds were characterized by IR, H
13
NMR, C NMR, and UV-Vis.
Keywords: Photochromic, Anthracene, Anthraquinone, Bis-1,3-diazabicyclo[3.1.0]hex-3-ene
Introduction
Photochromism is a phenomena defined as a reversible transformation between two isomeric species induced by
light. Photochromic compounds are interesting as their physical properties such as geometrical structures,
luminescence, optical rotation, absorption spectra, internal energy, viscosity, and refractive index, etc. can be
manipulated by light.
Synthesis and study of the photochromic compounds have attracted a great attention due to their significant
applications in optical data storage [1,2], optoelectronic devices [3,4], photo-switches and liquid-crystalline
actuators [5,6]. Spiropyrans [7,9], fulgides [10,11], diarylethenes [12,13], and azobenzenes [14,15] are most
known photochromic systems. Although a great numbers of photochromic compounds have been synthesized
that a few of them have shown photochromism in crystalline state. In continuation to our recent synthesis of
mono, bis- and tris-photochromic systems based on 1,3-diazabicyclo[3.1.0]hex-3-ene with considerable
photochromic properties both in solution and crystalline state [16-26], here, we report expansion of our
photochromic systems by incorporating anthracene backbone.
Results and Discussion
First, ketoaziridine compounds 4a-b was prepared according to our previous method as following: chalcones
were prepared by Claisen-Schmidt reaction, brominated in chloroform, and then transformed to the
corresponding ketoaziridines by reaction with NH
4
OAc (see supplementary data, Fig. S1) [16].
Second, anthracene dicarbaldehyde 10 was synthesized in a three-step reaction with some modification
according to the previous report [27]. In the first step, anthraquinone 5 was transformed to diepoxide 7 in the
1

presence of trimethylsolfunium iodide 6, NaH and DMSO under argon atmosphere. Diepoxide 7 was reacted
with LiBr in CH CN under reflux to produce 10-(hydroxyl methyl)anthracen-9-carbaldehyde 9.
3
In the third step, anthracene-9,10-dicarbaldehyde 10 was prepared by utilizing a new selective oxidation method
using ammonium chromate and ferric hydrogen sulfate in presence of wet silica gel to oxidize the hydroxyl
group of 9 to aldehyde without further oxidation of the other aldehyde group [28,29] (Scheme 1).
Scheme 1. Synthesis of dialdehyde 10 from 5
+
We can propose that ferric hydrogen sulfate and wet silica gel is able to produce H which will produce chromic
-
acid (HCrO
4
) in the reaction with ammonium chromate. The produced chromic acid can oxidize benzylic
alcohol to corresponding aldehyde. The proposed mechanism for oxidation of 9 to anthracene-9,10-
dicarbaldehyde 10 was shown in supplementary data (Fig. S2).
The IR spectra of diepoxide 7 indicated disappearance of C=O stretch and appearance of four absorption bands
-
1
1
at 1318, 896, 916, and 840 cm due to epoxy C-O-C stretch. The H NMR spectra displayed a singlet of 4
13
protons intensity at 3.27 ppm in addition to aromatic protons. Its C NMR spectra exhibited 5 types of carbon
atom; signals at 54.5 and 63.8 ppm which are indications of methylene and quaternary aliphatic carbon,
-
respectively. The IR spectra of 9 reveals the presence of OH and aldehyde carbonyl stretch at 3400 and 1675 cm
1
1
,
respectively. In the H NMR spectra of 9, hydroxyl, methylene, and aldehyde protons appeared as singlets at
3
.43, 5.75, and 11.54 ppm, respectively. The IR spectra of anthracene-9,10-dicarbaldehyde 10 showed
2

-
1
1
absorption of C=O at 1670 cm . The H NMR spectra displayed a singlet of 2 protons intensity at 11.51 ppm in
addition to other aromatic protons.
Several photochromic products 11-14 were prepared via 3-multicomponent reaction of 8 and 9 with
4
ketoaziridines 4 and excess NH OAc at room temperature, respectively (Scheme 2). Formation of these
1
13
compounds was confirmed on the basis of their IR, H NMR, and C NMR spectra.
Scheme 2. Preparation of photochromic compounds 11-16.
The IR spectra of compounds 11 and 12 confirmed disappearance of N-H and C=O groups in the starting
-
1
1
materials and appearance of C=N stretching band at 1600 cm . The H NMR spectra of compounds 11 and 12
showed signals at 2.86-3.82 ppm due to aziridine protons, imidazole protons appeared at 7.80 and 7.81 ppm as
singlet, aromatic and anthracene protons appeared at expected chemical shifts. Further support for the structure
13
of 11 and 12 was provided by C NMR spectra, which exhibits signals at121.6-148.1 ppm for aromatic carbons,
olefinic carbon appeared at 168.3 and168.4 ppm and aliphatic carbons appeared at 40.7-95.6 ppm.
3

-
1
In the IR spectra of compounds 13 and 14 an absorption band appeared at region 3400-3428 cm due to O–H
-
1
stretch, absorption band at 1600 cm indicates the presence of C=N, and absorption band at region 1040-1045
-
1
1
cm specify the presence of C-O bond. The H NMR spectra of compounds 13 and 14 displayed signals of
aziridine ring protons at regions 2.83-3.83 ppm, signal of methylene group at 5.68 and 5.72 ppm, signal of OH
group at 3.41 ppm, signal of imidazole protone at 7.77 and 7.83 ppm, and anthracene protons at 7.55-8.81 ppm
13
respectively. In C NMR spectra olefinic carbon appeared at 108.2 and 168.2 ppm, aromatic carbons appeared
at 121.4-148 ppm, and aliphatic carbons appeared at 40.6-95.6 ppm.
Two bis-photochromic products 15-16 were prepared via the reactions of premade 10 with two moles
4
ketoaziridines 4 and excess NH OAc at room temperature.
-
1
In the IR spectra of bis-photochromic 15 and 16 absorption bands at 1604-1614 cm are indication of C=N
1
functional group. The H NMR analysis of 15 and 16 showed signals of aziridine protons as singlet at 2.83-3.88
ppm, signal of imidazole proton at 7.81 and 7.84 ppm, aromatic and anthracene protons at 8.40-7.25 and 7.67-
1
3
8
.77 ppm, respectively. In C NMR spectra olefinic carbon for both of them appeared at 169.8 ppm, aromatic
carbons appeared at 121.6-148.2 ppm, and aliphatic carbons appeared at 40.8-95.8 ppm. These photochromic
derivatives in their NMR spectra at room light showed only structure of close-ring photoisomers. This can be
due to the more stability of the close-ring photoisomer in the presence of anthracene ring. According to our prior
experiences, appearance of the singlet signals with lower intensity in the vicinity of aziridine protons and singlet
signal at 6.0-7.0 ppm attributable to imidazoline proton that proved the formation of the open-ring photoisomer
[
20,22,24-25]. These statements are included in the revised manuscript and indicated as red pen in the text.
Photochromic compounds 11, 13, and 15 showed strong color change upon exposure to sun light in crystalline
state, while compounds 12, 14, and 16 did not show obvious color change in crystalline form. For 11 upon
exposure to sun light a color change from yellow to green was observed and for 13 yellow to bright brown and
for 15 yellow to bright green and by further exposure changed to dark green were observed. This can be due to
the resonance in these compounds; for para NO
2
derivatives 11, 13, and 15 the resonance is better and longer
than meta NO derivatives 12, 14, and 16. Also, increasing of the color intensity can be due to enhancement of
2
population of open form rather than closed form.
The formation of open-ring photoisomer and photochromic behavior of compounds 11-16 were confirmed by
UV-Vis spectra in EtOH under irradiation with UV light at 254 nm for different times. After UV irradiation, the
ethanolic solutions promptly turned to yellow color and the absorbance band at visible region emerged and
increased due to the formation of the open-ring photoisomer. The maximum absorptions are shown in Table 1.
All compounds showed isosbestic points in their UV-Vis studies which means that the close-ring and open-ring
photoisomers are in equilibrium at this wavelength. The isosbestic points for compounds 11, 13, and 15 are
higher than the others; it might be due to the nitro group.
4

A
B
Table 1. Spectra and data of λ max, λ max , λisosbestic for products 11-16
A
B
Compound
λ
max (nm)
λ
max (nm)
λ
isosbestic
1
1
2
205, 253.5, 350, 368, 388
206, 256, 351, 369, 389
205, 254, 368, 389, 431
256, 363, 424
301
1
296
13
14
15
16
205, 259, 356, 375, 396
205, 256, 339, 355, 375, 396
206, 253, 379, 398
205, 259, 375, 396, 436
206, 258, 356, 376, 396
205, 253, 410
302
264
313
280
212, 256, 360, 378, 400
208, 253, 365
A
B
λ
max: before irradiation, λ max: after irradiation
A
B
More important the comparison of λ max, λ max , λisosbestic for 11 and 15 with our previous synthesized 20 and 21
with phenyl as an alternative of anthracene [17,18, 20] exhibit a better photocoloration/photobleaching ratio and
acceptable light sensitivity due to continuous red shift absorption up to 400 nm (Fig. 1) (Table 2) .
Fig. 1. Structure of 20 and 21 with phenyl as an alternative of anthracene
A
B
Table 2. Spectra and data of λ max, λ max , λisosbestic for products 20 and 21
A
B
Compound
λ
max (nm)
λ
max (nm)
λ
isosbestic (nm)
318
2
0
1
281
401
2
207, 251
207, 261, 405
238
A
B
λ
max: before irradiation, λ max: after irradiation
A UV-Vis spectrum of compound 11 is depicted in Fig. 2. The compound was exposed to the UV light and its
absorption was recorded by 20 seconds intervals. The study showed that by increasing the UV irradiation time
the intensity of absorption increased while after 120 seconds it decreased. This phenomenon indicates that in
solution the photochromic properties of these compounds have lower repeatable cycle than in the solid form.
Also, a well-defined isosbestic point at 301 nm is observed (Fig. 2).
5

Fig. 2. Photochromic performance and UV-Vis spectra of 11 before and after UV light irradiation for different
-
4
times in EtOH (C = 1.0 × 10 M, 293 K).
Fig. 3 shows the UV-Vis spectra of 15 with two photochromic center in EtOH. The UV-Vis spectra were
recorded in 20 seconds intervals, and similar to 11 its intensity decreased after 120 seconds. Compound 15
exhibited λAmax at 206 and 253 nm before irradiation and λBmax at 206, 253 and 410 nm after irradiation.
Isosbestic point revealed at 313 nm.
6

Ar
Ar
Ar
Ph
Ar
N
N
N
N
Ph
Ar
UV
N
N
N
N
Ph
Ar
UV
N
N
N
N
Vis / heat
Ph
Ph
Vis / heat
Ph
1
5
close-open ring (pale green)
open-open ring (green)
close-ring (yellow)
0
Sec
10 Sec
20 Sec
Fig. 3. Photochromic performance and UV-Vis spectra of 15 before and after UV light irradiation for various
-
4
times in EtOH (C = 1.0 × 10 M, 293 K).
Experimental Section
Chemicals were purchased from Fluka and Merck. Melting points were uncorrected and determined by
1
13
Electrothermal 9100 melting point apparatus. Products were characterized by m. p., IR, H NMR, C NMR and
TLC. IR spectra were obtained on a Shimadzu IR-470. All NMR data were recorded in CDCl using Bruker
3
Avance 500 MHz and 400 MHz spectrometer. Chemical shifts are reported in ppm (δ) using deuterated solvents
as internal references. The UV-Vis absorption spectra in the range 200-600 nm (EtOH) as well as position of
A
B
λ
max for the initial A (λ max nm) and photoinduced B (λ max nm) photoisomers were measured with a Shimadzu
UV-2100 spectrophotometer. Plate chromatography was conducted over silica gel 60, F254 Merck.
Preparation of trans-dispiro[oxirane-2,9′[10′H]-anthracene-10′,2″-oxirane] 7:
To a two-necked flask NaH (13 mmol, 0.52 g, 60% in oil) was added under argon atmosphere and washed with
n-hexane (3×20 mL). Then trimethylsolfunium iodide (12.64 mmol, 2.58 g) in dry DMSO (30 mL) was added
slowly in darkness. The mixture was stirred for 8 hours at rt. After that, anthraquinone (5.62 mmol, 1.17 g) in
dry DMSO (30 mL) was added and stirred for 16 hours at rt. After completion of the reaction, flask was put onto
an ice bath; crushed ice (100 g) was added to the mixture and stirred for 30 min at 0˚C. The white or yellow
7

˚
precipitate was filtered off, washed with water and dried. Yield 80%. m. p. 117-120 C, colorless solid, IR (KBr,
-1
1
ν/cm ): 3040, 2980, 1479, 1450, 1318, 916, 896, 840, 762, 740. H NMR (400 MHz, CDCl
3
, ppm): δ 3.27 (s,
1
3
4
H, CH ), 7.29-7.44 (m, 8H, H , H ). C NMR (100 MHz, CDCl , ppm): δ 54.5, 63.8, 122.3, 128.4, 135.4.
2 b c 3
Preparation of 10-(hydroxymethyl) anthracene-9-carbaldehyde 9:
To a solution of LiBr (23 mmol, 2 g) in dry CH CN (80 mL) was added 7 (5 mmol, 1.18 g) and stirred for 18
3
hours in darkness at rt. After completion of the reaction, flask was put onto an ice bath and cooled down to -20
°
˚
C. Golden crystals gradually formed upon cooling, filtered off and dried on air. Yield 80%. m. p. 180-182 C,
-
1
1
golden crystals, IR (KBr, ν/cm ): 3400, 2950, 2900, 2750, 2700, 1675, 1620, 1540, 1030, 750. H NMR (400
MHz, CDCl , ppm): δ 3.43 (s, 1H, OH), 5.75 (s, 2H, CH ), 7.68-7.74 (m, 4H, H , H ), 8.57 (d, J = 8.0 Hz, 2H,
), 8.94 (d, J = 8.0 Hz, 2H, H ), 11.54 (s, 1H, CHO).
3
2
b
c
H
d
a
Preparation of 9,10-anthracenedicarbaldehyde 10:
To flask containing (NH Cr (1 mmol, 0.252 g), wet silica gel (0.3 g) and Fe(HSO
dry CH CN (5 mL) was added compound 9 (1 mmol, 0.236 g) and refluxed for 3 hours. The mixture was filtered
off and washed with CH CN (3×3 mL). The organic layer was dried with MgSO , filtered and evaporated under
)
4 2
O
2 7
4 3
) (1 mmol, 0.347 g) in
3
3
4
°
-1
reduced pressure. Yield 60%. m. p. 237-240 C, orange solid, IR (KBr, ν/cm ): 3068, 2921, 2850, 2780, 1670,
1
1
3
586, 1445, 752, 695. H NMR (400 MHz, CDCl
3
, ppm): δ 7.73 (dd, J = 5.8, 3.4 Hz, 4H, H
b
), 8.76 (dd, J = 5.6,
a
.6 Hz, 4H, H ), 11.51 (s, 2H, CHO).
Preparation of 2-(anthracene-9-yl)-6-(4-nitrophenyl)-4-phenyl-1,3-diazabicyclo[3.1.0]hex-3-ene 11:
A solution of 4a (1 mmol, 0.268 g), 8 (1 mmol, 0.236 g) and NH OAc (5 mmol, 0.4 g) in dry DMF (3 mL) was
4
stirred at rt for 24 hours. The reaction was monitored by TLC (EtOAc/ether, 6/3). After completion of the
reaction, the mixture was collected by filtration, washed with EtOH (60 ˚C) and dried. The crud product was
°
recrystallized from EtOH. After irradiation with UV it converted to light green. Yield 76%. m. p. 191-193 C,
-
1
1
yellow solid, IR (KBr, ν/cm ): 3040, 2980, 2880, 1600, 1510, 1470, 1440, 1340, 830, 720, 690. H NMR (400
MHz, CDCl , ppm): δ 2.84 (s, 1H, H ), 3.82 (s, 1H, H ), 7.25 (d, J = 8.8 Hz, 2H, H ), 7.48 (t, J = 7.4 Hz, 2H,
), 7.55 (broad, 2H, H ), 7.61-7.70 (m, 3H, H , H ), 7.80 (s, 1H, H ), 7.99 (d, J = 8.8 Hz, 2H, H ), 8.02 (d, J =
.4 Hz, 2H, H ), 8.19 (d, J = 8 Hz, 2H, H ), 8.50 (s, 1H, H ); C NMR (100 MHz, CDCl
3
1
2
b
H
h
g
e
d
4
c
13
8
a
i
j
), 8.72 (broad, 2H, H
f
3
,
ppm): δ 40.9, 55.7, 95.6, 123.4, 124.8, 125.6, 126.6, 127.4, 128.3, 128.6, 129.2, 129.6, 130.9, 131.6, 132.0,
1
45.3, 147.0, 168.4; UV-Vis (EtOH) λmax/nm: 205.0, 253.5, 350.0, 368.0, 388.5 nm before irradiation and 205.0,
53.5, 350.0, 368.0, 388.5, 430.34 nm after irradiation. HRMS ((+)-ESI): m/z = 455.1641 (calcd. 455.1634 for
2
30 21 3 2
C H N O ).
Preparation of 2-(anthracene-9-yl)-6-(3-nitrophenyl)-4-phenyl-1,3-diazabicyclo[3.1.0]hex-3-ene 12:
A similar procedure for synthesis of 12 as described for 11 was applied compounds 8 and 4b were used. The
reaction completed over 5 days. After irradiation with UV light its color did not changed obviously. Yield 65%.
°
-1
m. p. 143-145 C, cream solid, IR (KBr, ν/cm ): 3050, 2980, 2880, 1600, 1508, 1470, 1442, 1340, 830, 740, 690.
1
3 1 2 c
H NMR (400 MHz, CDCl , ppm): δ 2.86 (s, 1H, H ), 3.82 (s, 1H, H ), 7.27-7.30 (t, J = 7.6 Hz, 1H, H ), 7.39 (d,
8

J = 7.6 Hz, 1H, H
), 7.96 (d, J = 8 Hz, 2H, H
s, 1H, H ), 8.74 (broad, 2H, H
25.6, 126.6, 127.3, 128.4, 128.6, 129.07, 129.10, 129.13, 129.5, 131.0, 131.6, 131.9, 132.0, 132.8, 134.2, 140.1,
48.1, 168.4; UV-Vis(EtOH) λmax/nm: 206.0, 255.5, 351.0, 368.5, 388.5 nm before irradiation and 206.0, 255.5,
62.5, 423.22 nm after irradiation. HRMS ((+)-ESI): m/z = 455.1639 (calcd. 455.1634 for C30 ).
d
), 7.48 (t, J = 7.2 Hz, 2H, H
j
), 7.55 (broad, 2H, H
), 8.05 (s, 1H, H
); C NMR (100 MHz, CDCl , ppm): δ 40.7, 55.5, 95.6, 121.62, 122.2, 124.8,
i
), 7.62-7.69 (m, 3H, H
f
, H
g
), 7.81 (s, 1H,
H
4
e
), 8.02 (d, J = 8.4 Hz, 1H, H
b
a
), 8.20 (d, J = 7.6 Hz, 2H, H
k
), 8.50
13
(
l
h
3
1
1
3
21 3 2
H N O
Preparation of (10-(6-(4-nitrophenyl)-4-phenyl-1,3-diazabicyclo[3.1.0]hex-3-en-2 -yl)anthracene-9-yl)methanol
3: A similar procedure as described for 11, for synthesis of 13 was applied compound 9 was used instead of 8
1
°
-1
with 4a. The reaction completed over 3 days. Yield 70%. m. p. 190-192 C, yellow solid, IR (KBr, ν/cm ): 3400,
1
3
050, 2910, 2850, 1600, 1510, 1490, 1440, 1340, 1040, 800, 740, 695. H NMR (400 MHz, CDCl
3
, ppm): δ 2.83
), 7.55-7.57 (m, 4H,
), 8.18 (d, J = 8.4 Hz, 2H, H ),
, ppm): δ 40.7, 55.6, 57.7, 95.6,
(s, 1H, H
1
), 3.41 (s, 1H, OH), 3.80 (s, 1H, H
), 7.61-7.68 (m, 3H, H , H ), 7.77 (s, 1H, H
), 8.79 (broad, 2H, H
2 2 b
), 5.68 (s, 2H, CH ), 7.23 (d, J = 8.8 Hz, 2H, H
H
h
, H
g
d
e
4
), 7.97 (d, J = 8.8 Hz, 2H, H
c
a
13
8
1
1
3
.47 (d, J = 8 Hz, 2H, H
i
f
); C NMR (100 MHz, CDCl
3
23.4, 124.4, 125.8, 126.2, 126.4, 127.3, 128.6, 129.2, 130.0, 130.2, 130.8, 131.9, 132.0, 133.2, 145.1, 147.0,
68.2; UV-Vis (EtOH) λmax/nm: 204.5, 258.5, 356.0, 374.5, 395.5 nm before irradiation and 204.5, 258.5, 356,
23 3 3
74.5, 395.5, 435.9 nm after irradiation. HRMS ((+)-ESI): m/z = 485.1734 (calcd. 485.1739 for C31H N O ).
Preparation of (10-(6-(3-nitrophenyl)-4-phenyl-1,3-diazabicyclo[3.1.0]hex-3-en-2 -yl)anthracene-9-yl)methanol
4: A similar procedure as described for 11, for synthesis of 14 was applied compound 9 and 4b were used. The
reaction completed over 5 days. After irradiation with UV light its color did not changed obviously. Yield 50%.
1
°
-1
m. p. 150-153 C, yellow solid, IR (KBr, ν/cm ): 3428, 3063, 2962, 1604, 1515, 1446, 1344, 1045, 862, 800,
1
6
7
1
8
1
95. H NMR (400 MHz, CDCl
3
, ppm): δ 2.83 (s, 1H, H
), 7.41 (d, J = 7.6, 1H, H ), 7.56-7.59 (broad, 4H, H
), 8.01 (d, J = 8 Hz, 2H, H ), 8.18 (d, J = 8.4 Hz, 2H, H ), 8.24 (s, 1H, H
); C NMR (100 MHz, CDCl , ppm): δ 40.6, 55.4, 57.7, 95.5, 121.4, 122.0, 124.4, 125.9,
26.2, 126.4, 127.4, 128.6, 129.2, 130.0, 130.2, 130.8, 131.9, 132.0, 133.2, 134.2, 140.1, 148.0, 168.2; UV-Vis
EtOH) λmax/nm: 205.0, 256.0, 338.5, 355.0, 375.0, 395.5 nm before irradiation and 206.0, 257.5, 356.0, 375.7,
95.5 nm after irradiation. HRMS ((+)-ESI): m/z = 485.1743 (calcd. 485.1739 for C31 ).
1
), 3.41 (s, 1H, OH), 3.83 (s, 1H, H
, H ), 7.62-7.68 (m, 4H, Hf,g), 7.83 (s,
), 8.47 (d, J = 8 Hz, 2H, H ),
2 2
), 5.72 (s, 2H, CH ),
.25-7.29 (t, 1H, H
H, H
.81 (broad, 2H, H
c
d
i
j
4
e
b
a
k
13
h
3
(
3
23 3 3
H N O
Preparation of 9,10-bis(6-(4-nitrophenyl)-4-phenyl-1,3-diazabicyclo[3.1.0]hex-3-en-2-yl) anthracene 15:
A similar procedure as described for 11, for synthesis of 15 was applied, however compound 10 1 eq with 2eq 4a
4
and 2eq NH OAc were used. The reaction completed over 7 days. After irradiation with UV light it converted to
°
-1
bright green. Yield 70%. m. p. 198-200 C, yellow solid, IR (KBr, ν/cm ): 3052, 2934, 1604, 1513, 1440, 1343,
1
8
45, 734, 695. H NMR (400 MHz, CDCl
3
, ppm): δ 2.84 (s, 2H, H
), 7.67 (dd, J = 5.6, 3.6 Hz, 4H, H ), 7.81 (s, 2H, H
); C NMR (100 MHz, CDCl , ppm): δ 41.0, 55.9, 95.8, 123.4,
1
), 3.82 (s, 2H, H
2
), 7.25 (d, J = 8.4 Hz, 4H,
H
b
), 7.49-7.58 (m, 6H, H
e
, H
d
g
4
), 8.02 (d, J = 8.4 Hz, 4H, H
c
),
13
8
1
.20 (d, J = 8.4 Hz, 4H, H
a
), 8.74 (broad, 4H, H
f
3
25.7, 126.6, 127.4, 128.6, 129.3, 130.7, 131.6, 132.0, 145.5, 147.3, 169.8. UV-Vis (EtOH) λmax/nm: 205.5,
9

2
53.0, 379.0, 398.0 nm before irradiation and 205.0, 253.0, 409.5 after irradiation. HRMS ((+)-ESI): m/z =
32.2491 (calcd. 732.2485 for C46 ).
7
32 6 4
H N O
Preparation of 9,10-bis(6-(3-nitrophenyl)-4-phenyl-1,3-diazabicyclo[3.1.0]hex-3-en-2-yl) anthracene 16:
A similar procedure as described for 15, for synthesis of 16 was applied, compounds 10 and 4b were used. The
reaction completed over 7 days. After irradiation with UV light its color did not changed obviously. Yield 65%.
°
-1
m. p. 149-151 C, yellow solid, IR (KBr, ν/cm ): 3060, 2964, 1614, 1528, 1445, 1394, 1348, 879, 803, 734, 692.
1
H NMR (100 MHz, CDCl
), 7.47 (m, 6H, H , H ), 7.67 (dd, J = 5.4, 3.4 Hz, 4H, H
J = 8.4 Hz, 2H, H ), 8.20 (s, 2H, H ), 8.77 (broad, 4H, H
5.8, 121.6, 122.3, 125.7, 126.6, 127.4, 128.6, 129.3, 130.7, 131.7, 132.1, 133.1, 134.0, 140.5, 148.2, 169.8; UV-
Vis (EtOH) λmax/nm: 212, 255.5, 359.5, 378, 399.5 nm before irradiation and 208, 252.5, 358.5 nm after
3
, ppm): δ 2.83 (s, 2H, H
1
), 3.88 (s, 2H, H
2
), 7.29 (t, 2H, H
), 8.04 (d, J = 8 Hz, 4H, H
); C NMR (100 MHz, CDCl , ppm): δ 40.8, 55.8,
c
), 7.34 (d, J = 7.6 Hz, 2H,
H
d
f
g
i
), 7.84 (s, 2H, H
4
e
), 8.16 (d,
13
b
a
h
3
9
32 6 4
irradiation. HRMS ((+)-ESI): m/z = 732.2489 (calcd. 732.2485 for C46H N O ).
Conclusion
In summary, anthracene-9-carbaldehyde, 10-(hydroxymethyl)anthracene-9-carbaldehyde and 9,10-anthracene
dicarbaldehyde was used in synthesis of mono- and bis-photochromic compounds successively. The
photochromic compounds showed color change in crystalline state and also their wavelength change under UV
irradiation in EtOH solution that confirms their photochromic behavior.
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GRAPHICAL ABSTRACT
Synthesis of Anthracene Derivatives of 1,3-Diazabicyclo[3,1,0]hex-3-ene
Nosrat O. Mahmoodi, Safoura Mirkhaef
13

Highlight for Reviewer
•
•
Synthesis of mono- and bis- 1,3-diazabicyclo[3.1.0]hex-3-enes with anthracene moiety
Photochromic behavior of both mono- and bis- compounds
•
•
Photochromic behavior in solution and in solid state
irradiation under UV light at 254 nm.
14