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Medical Mass Spectrometry Vol. 4 No. 1

Research Paper

Chemical modiﬁcation of imipramine and desipramine
1

2

2

1

Hideki Hayashi *, Tadashi Ogawa , Hiroshi Seno , Yuzo Ishigaki , Mitsuo Oda
1

1

Nagoya Municipal Industrial Research Institute, 3‒4‒41 Rokuban, Atsuta-ku, Nagoya, Aichi 456‒0058, Japan
2
Aichi Medical University, 1‒1 Yazakokarimata, Nagakute, Aichi 480‒1195, Japan
Chemical modiﬁcation of imipramine and desipramine, which have pharmaceutical applications such as an an-

Abstract

tidepressant was carried out. Dibromoimipramine and dibromodesipramine were prepared from imipramine hydrochloride
and desipramine hydrochloride, respectively. Dibromodesipramine was reacted with di-tert-butyl dicarbonate to prepare
N-Boc type compound. ESI-MS of the dibromides showed typical MS signals of dibromides. Polymerizations of the dibromides by the nickel-promoted coupling reaction aﬀorded corresponding polymers. These results suggest that chemical
modiﬁcation of imipramine and desipramine expected to develop another functional material.
Key words: imipramine, desipramine, dibromide, polymerization

Introduction

can also be expected to be functional for medical materials

Triclinic compounds have been widely used as medical

as well. These polymers are prepared from corresponding. As a triclinic compound, we focused imipraminedibromides as monomers, which seems to be easy to check

1‒5)

drugs

(Imip, Fig. 1)

6,7). It is known that metabolization of Imip
7,8)

their structure by MS because their molecular weight is9‒11), Fig. 1) . On the other hand,these materials are ethylene unit-bridged diphenylamine

observed as three molecular ion peaks at ±2 at their motherderivatives with alkylamine substituent on the N atom of

the dibromide with other analysis methods (NMR, IR, etc)

their diphenylamine unit. Diphenylamine with bridged
units has been of interest for functional materials. We previ-

will be expected.

aﬀords desipramine (Desimolecular ion peak. Therefore, more detailed analysis of

In this manuscript, we here report results of MS analysis
of dibromoimipramine and dibromodesipramine deriva-

ously reported the preparation, properties, and applications
12,13)
12,13), sulfone (‒SO‒), monosilaneof sulfur (‒S‒)
14‒24)

tives. As chemical modiﬁcation of imipramine and desipramine, we also tried polymerization of the dibromides deriv-

15,23‒25), disilane (‒SiMe2SiMe2‒), and disilox(‒SiR2‒)
15,24)
unit-bridged diphenylamineane (‒SiMe2OSiMe2‒)

atives as monomers to prepare imipramine or desipramine

derivatives.

homopolymers.

We also prepared ethylene-bridged diphenylamine-con26‒30). Diphenylamine with bridged unit
can be expected as materials for bio-conjugation such as

taining polymers
DNA

14‒17)

18,19,26‒30), or biodegradable plastics. Therefore it* Corresponding author
Hideki Hayashi

Nagoya Municipal Industrial Research Institute, 3‒4‒41
Rokuban, Atsuta-ku, Nagoya, Aichi 456‒0058, Japan

Tel: ＋81‒52‒654‒9912, Fax: ＋81‒52‒654‒6788
E-mail: hayashi.hideki@nmiri.city.nagoya.jp

Received: November 27, 2019. Accepted: March 5, 2020.
Epub April 28, 2020.
Fig. 1.

DOI: 10.24508/mms.2020.06.002
50

Diphenylamine with bridging unit.

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Medical Mass Spectrometry Vol. 4 No. 1

Materials and Methods

Preparation of 2,8-dibromo-10,11-dihydro-5-[3-(N-methylN-t-butoxycarbonylamino)propyl]-5H-dibenz[b,f]azepine

Reagents and measurements

2,8-dibromoimipramine hydrochloride (2,8-dibromo-10,11dihydro-5-[3,3-di(methylamino)propyl]-5H-dibenz[b,f]aze-(BrDesiBoc)
BrDesi (0.79 g, 1.86 mmol) and di-tert-butyl dicarbonate(Boc2O, 1.10 g, 5.04 mmol) was dissolved to 20 mL of ace-pine hydrochloride, BrImipHCl) and 2,8-dibromdesipramine hydrochloride (2,8-dibromo-10,11-dihydro-5-[3-(methyl26)

amino)propyl]-5H-dibenz[b,f]azepine

tonitrile and N,N-dimethylaminopyridine (DMAP, 22.4 mg,hydrochloride,

were prepared by the reported procedures.

0.18 mmol) was added to the mixture. The mixture wasstirred overnight, then the solvent was evaporated. The resi-

Other chemicals were also used as purchased. NMR spectra

due was puriﬁed by silica gel column chromatography.

were taken by using a Varian INOVA400 spectrometer, andIR spectra were taken by using a JASCO FT/IR-410 spec-

BrDesiBoc (0.78 g, 1.49 mmol) obtained as a light brown

BrDesiHCl)27)

liquid. Yield was 80%.
1
H-NMR (CDCl3): δ 7.2‒7.3 (m, 4H), 6.89 (d, 2H, J＝trometer. UV-visible spectra were measured with a JASCO
V-570DS spectrometer.

9.4 Hz), 3.63 (t, 2H, J＝6.8 Hz), 3.18 (br, 2H), 3.08 (s, 4H),
13
2.74 (br, 3H), 1.6‒1.8 (m, 2H), 1.38 (s, 9H) ppm. C-NMR

Shimadzu LCMS-8040 mass spectrometer and Shimadzu
NexeraX2 LC system (Shimadzu Co., Kyoto, Japan) wereused for ESI-MS analysis.

(CDCl3): δ 146.41, 135.72, 132.11, 128.99, 128.94, 121.25,

Preparation of the compounds

2,8-dibromo-10,11-dihydro-5-[3-(dimethylamino)propyl]-5H-dibenz[b,f]azepine (BrImip)

Reaction of BrDesiBoc and triﬂuoroacetic acid

Preparation

BrDesiBoc (305 mg) was dissolved in triﬂuoroacetic acid
(TFA, 3 mL) and the solution was stirred at room tempera-

115.11, 78.95, 47.84, 33.92, 31.25, 28.02, 25.79 ppm.

of

NaOH (0.64 g, 16 mmol) was added to BrImipHClture for 2 h. The solution was poured into water (5 mL) and(0.51 g, 1.07 mmol) in water and the mixture was stirred for

NaOH (0.52 g) was added to the solution. The solution was

2 h. Then, the mixture was extracted by ether, and theextracted by ether and the organic layer was washed inorganic layer was washed in brine and dried over MgSO4.

NaOH aq and brine. Then, the organic layer was dried over

After removal of MgSO4 by ﬁltration, the solvent was

MgSO4. After removal of MgSO4 by ﬁltration, the solvent

removed by evaporation. BrImip was obtained as a yellow

was removed by evaporation. 134 mg of light brown liquid

liquid. Yield was 84%.
1
H-NMR (CDCl3): δ 7.2‒7.3 (m, 4H), 6.93 (d, 2H, J＝9.4

was obtained.

Hz), 3.69 (t, 2H, J＝7.0 Hz), 3.10 (s, 4H), 2.28 (t, 2H, J＝7.2
13Hz), 2.16 (s, 6H), 1.6‒1.8 (m, 2H) ppm. C-NMR (CDCl3):

Preparation of polymers

Preparation of poly(10,11-dihydro-5-[3-(dimethylamino)propyl]-5H-dibenz[b,f]azepine-2,8-diyl) (PImip)

δ 146.86, 136.00, 132.36, 129.28, 121.77, 115.27, 57.36,

Under nitrogen, toluene (5 mL) solution of BrImip

48.93, 45.49, 31.61, 25.92 ppm.

(370 mg, 0.84 mmol) was added to a mixture of Ni(cod)2

of 2,8-dibromo-10,11-dihydro-5-[3-(methylamino)propyl]-5H-dibenz[b,f]azepine (BrDesi)(340 mg, 1.24 mmol, cod＝1,5-cyclooctadiene), cod (1 mL)-bipyridyl (bpy, 190 mg, 1.22 mmol) in tolueneand 2,2′

Reaction of BrDesiHCl (1.38 g, 3.00 mmol) and NaOH

(5 mL) and the mixture was heated at 60°
C for 48 h. A

(0.53 g, 13.25 mmol) by the same preparation method of

black powder precipitated upon pouring the mixture into

BrImip resulted BrDesi (1.18 g, 2.78 mmol) as a lightmethanol was successively washed with water, methanol,brown liquid. Yield was 93%.
1
H-NMR (CDCl3): δ 7.2‒7.3 (m, 4H), 6.92 (d, 2H, J＝and hexane. As colorless powder, 146 mg (0.52 mmol

Preparation

monomer unit) of PImip was obtained. Yield was 62%.
H-NMR (CDCl3): δ 6.8‒7.6 (m, 6H), 3.80 (2H), 3.21 (4H),1

7.0 Hz), 2.36 (s, 3H), 1.6‒1.8 (m, 2H) ppm.

9.4 Hz), 3.70 (t, 2H, J＝6.8 Hz), 3.09 (s, 4H), 2.56 (t, 2H, J＝
13
C-NMR

2.32 (2H), 2.17 (6H), 1.77 (2H).

(CDCl3): δ 146.71, 135.89, 132.25, 129.16, 121.63, 115.18,

147.01, 134.99, 134.13, 128.15, 124.75, 120.18, 57.43,

49.49, 48.56, 36.43, 31.47, 27.75 ppm.

48.75, 45.05, 32.45, 25.57 ppm.

51

C-NMR (CDCl3): δ

13

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from commercially available products imipramine hydro-(10,11-dihydro-5-[3-(N-methyl-N-tbutoxycarbonylamino)propyl]-5H-dibenz[b,f]azepine-2,8-Preparationofchloride(ImipHCl)anddesipraminehydrochloride

Reaction of 1.17 g (2.23 mmol) of BrDesiBoc with 0.74 g(DesiHCl) by the reported method for bromination of31)
N-methyldiphenylamine . ESI-MS of BrImipHCl andof Ni(cod)2 and 0.42 g of bpy aﬀorded 730 mg (2.0 mmol
1
monomer unit) of PDesiBoc. Yield was 90%. H-NMR

BrDesiHCl were shown in Fig. 2(a) and 2(b). As shown inthe ﬁgures, typical molecular ion peaks assigned as dibro-diyl) (PDesiBoc)(CDCl3): δ7.0‒7.4 (m, 6H), 3.78 (2H), 3.23 (6H), 2.75 (3H),
13
1.82 (2H), 1.38 (9H). C-NMR (CDCl3): δ 155.73, 147.93,

mide was observed. When HCl of BrImipHCl and

135.01, 134.17, 128.15, 124.81, 120.05, 79.23, 48.20, 46.57,

3(a)), HCl in BrImipHCl and BrDesiHCl was removed

34.26, 32.41, 28.39, 26.42 ppm.

and BrImip and BrDesi were obtained as viscous liquid,
respectively. ESI-MS of BrImip (Fig. 2(c)) and BrDesi

BrDesiHCl were neutralized by base like NaOH (Fig.

＋

Preparation of (10,11-dihydro-5-[3-(methylamino)propyl]5H-dibenz[b,f]azepine-2,8-diyl) (PDesi)shown in Fig. 4, NMR signals based on aminoalkyl unit

PDesiBoc (228 mg) was dissolved in TFA (10 mL) andmoved to the high magnetic ﬁeld by reaction with NaOH.

the solution was stirred at room temperature for two days.

These changes of NMR shift seem to come from the change

The solution was poured into 30 mL of 3M NaOH aqueousof electronic state of alkylamine unit by removal of HCl.
The NH unit of BrDesi was converted to N-butoxycar-(Fig. 2(d)) showed molecular ion peaks as [M＋H] . As

solution to obtain precipitation and the precipitation waswashed in methanol. Drying under vacuum the precipita-

32)(Fig. 3(b)). As
shown in Fig. 5(b), IR spectrum of BrDesiBoc showed sig-bonyl (NBoc) by the reported proceduretion gave 119 mg of PDesi as white powder. As PDesi,
1yield was 72%. H-NMR (CDCl3): δ 7.0‒7.4 (m, 6H), 3.83

−1(2H), 3.23 (6H), 2.62 (2H), 1.82 (2H), 1.38 (9H).

which is assigned as ‒N‒CO‒O‒
unit by reaction of BrDesi (Fig. 5(a)) ESI-MS of

Results and Discussion

BrDesiBoc is shown in Fig. 2(e). As shown in the ﬁgure,the molecular ion peak also observed as typical for dibro-

nal at about 1690 cm

Preparation of dibromides
26)

BrImipHClmide such as BrImipHCl and BrDesiHCl. These results
27)

and BrDesiHClsuggest chemical structure of BrDesiBoc.

were prepared as solidFig. 2.

ESI-MS of the dibromides.
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Medical Mass Spectrometry Vol. 4 No. 1

Fig. 3.

Preparation scheme of dibromoimipramine and dibromodesipramine derivatives.

Fig. 4.

1

Change of the H NMR spectra of the dibromides by dehydrochlorination.

Fig. 6.

TG curve of BrDesiBoc. Analyzed under air.

It is known that Boc works as protective group of NH
Fig. 5.

33)

because NBoc is converted to NH unit by heating

IR spectra of BrDesi, BrDesiBoc, and reaction
product of BrDesiBoc.

32)

or

treatment of acid . Therefore, BrDesiBoc was heated to53

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Fig. 7.

Table 1.
Polymer

Polymer preparation scheme.

Results of polymerizations−3 ayield %

−3 a

Mw×10

Mn×10

Mw/Mn

PImip

62

2.6

2.1

1.2

PDesiBoc

90

10.1

6.5

1.5

a

Determined by GPC. Eluent was THF. Polystyrene standard.

150°
C and 200°
C, however, conversion of NBoc to NH wasnot observed (Fig. 5(c) and Fig. 5(d)). To investigate if

Fig. 8.

NBoc of BrDesiBoc can be converted, thermogravimetric

IR spectra of (a) PDesiBoc and (b) PDesi.

polymer was not completely clear. To prepare poly(arylene)
homopolymer with well-deﬁned structure, dehalogenative(TG) analysis was carried out, however, weight loss bycleavage of Boc was not observed like Boc-substituted dia(Fig. 6). Therefore, BrDesiBoc was treatedpolycondensations of aromatic dihalide by using organon-

with TFA. As shown in Fig. 2(f) and Fig. 5(e), the MS andthe IR spectrum of TFA-treated BrDesiBoc was same asickel process have been carried out . Therefore, this type

BrDesi. This result suggests that Boc of BrDesiBoc works

Results of polymerizations were shown in Table 1. PImip

32)

rylamines

34)

polymerizations are carried out as shown in Fig. 7(a).
and PDesiBoc were soluble in CHCl3 and THF. Solubility

as protective group of NH of desipramine unit.

of PImip prepared by this method became higher than

Polymerization of dibromides

PImip prepared by oxidative polymerization because of40)
forming well-deﬁned structure like poly(phenazasiline) .

It is known that coupling reaction of aromatic dihalide byusing organometallic compound can aﬀord relative poly-

As described above, the NBoc unit of the products expect

33‒37). We reported preparation of dibenzazepine-containing copolymers by Suzuki-Miyaura coupling reaction

to be converted to NH by TFA, therefore, PDesiBoc was

as correspond-

spectra by the reaction is shown in Fig. 8. As shown in the

mers

26)

by using BrImipHCl

27)

and BrDesiHCltreated with TFA as shown in Fig. 7(b). The change of IR

ing monomers.

ﬁgure, the signal assigned as originated from urea units at−1in PDesiBoc was disappeared due to thereaction. This suggest that Boc unit of PDesiBoc was com-

On the other hand, our group prepared PImip and PDesi

about 1690 cm

by oxidative polymerization of ImipHCl and DesiHCl,
29)
respectively . Oxidative polymerization is very conve-

pletely cleaved by TFA and PDesiBoc was converted tonient method for preparation of poly(arylene) type poly20,38,39)

mer

PDesi.

, however, sometimes the juncture of obtained

The optical data of the polymers and corresponding54

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Medical Mass Spectrometry Vol. 4 No. 1

Table 2.

Comparison of optical properties of the polymers and corresponding monomeric compoundsaR

PolymerMe

PImip

Absorptionb
λmax/nm

Fluorescenceb,cλmax/nm

321

410

Imip

256

d

259

d

406

Desi

404

DesiBoc

H

PDesi

321

Boc

PDesiBoc

321

a

MonomericacompoundbcAbsorptionb
λmax/nm259dChemical structure of the compounds are shown in Fig. 9(a). CHCl3 solution. Excited at absorption λmax. CHCl3 soluble part.

mides were carried out by polymerizations. Optical properties of the polymers were changed by polymerizations. The
compounds prepared in this manuscript are expected to
become medically functional materials such as for detection by ﬂuorometry and for bio-conjugation materials (likeDNA or biopolymers).

Conﬂict of Interest
The authors declare that we have no conﬂict of interest.

Acknowledgement

The authors thank to Prof. Yukio Onouchi (Aichi Insti-

tute of Technology: AIT), Mr. Masanobu Maeda (AIT), Mr.
Taiki Naruo (AIT), Mr. Hiroki Hirota (AIT), and Mr. Junpei Kuno (AIT) for their helpful supports.
A part of this work was performed under the Cooperative
Fig. 9.

Research Program of Network Joint Research Center for(a) Chemical structure of the polymers and corresponding monomeric compounds and (b) absorption and ﬂuorescent spectra of PImip and Imip.

Materials and Devices.
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