Synthesis and transformations of substituted 3,3′-diquinolinyl sulfides

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Synthesis and Transformations

of Substituted 3,3′-Diquinolinyl

Sulfides

Krystian Pluta ^a

^aDepartment of Organic Chemistry , The Medical

University of Silesia , Sosnowiec, Poland

Published online: 16 Aug 2006.

To cite this article: Krystian Pluta (2005) Synthesis and Transformations of

Substituted 3,3′-Diquinolinyl Sulfides, Phosphorus, Sulfur, and Silicon and the Related

Elements, 180:11, 2457-2475, DOI: 10.1080/104265090921191

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Phosphorus, Sulfur, and Silicon, 180:2457–2475, 2005

ISSN: 1042-6507 print / 1563-5325 online

DOI: 10.1080/104265090921191

Synthesis and Transformations of Substituted

3,3^ꢀ-Diquinolinyl Sulﬁdes

Krystian Pluta

Department of Organic Chemistry, The Medical University of Silesia,

Sosnowiec, Poland

Reactions of the 1,4-dithiin ring opening in 1,4-dithiinodiquinoline 1 with selected

oxygen nucleophiles followed by S- and N-alkylation led to sulﬁdes possessing one

or two quinolinyl or quinolonyl units. Diquinolinyl sulﬁdes 2 were transformed into

quinolinyl-quinolonyl sulﬁdes 3 or diquinolonyl sulﬁdes 9 via thermal rearrange-

ment (the O-N alkyl migration) or hydrolysis of the alkoxy and alkylthio groups

with the hydrochloric acid-ethanol mixture.

Keywords 1,4-dithiinodiquinoline; 4(1H)-quinolones; diquinolyl sulﬁdes; ring opening

INTRODUCTION

Substituted 4-quinolones are the quinoline derivatives of great inter-

est because of a broad spectrum of activity, mainly antibacterial¹and

recently anticancer activity.²⁻⁴Some substituted quinolinyl sulﬁdes

and disulﬁdes exhibit antibacterial,⁵⁻⁸antidepressant,⁹and very re-

cently, antiproliferative activity.^10,11Whereas 2,2^ꢀ- and 4,4^ꢀ-diquinolinyl

sulﬁdes most often were synthesized from substituted 2- and 4-

haloquinolines, synthesis of other x,x-diquinolinyl sulﬁdes (x = 2–4) is

fatiguing and troublesome.¹²Our original conception of the 1,4-dithiin

ring opening reactions in isomeric 1,4-dithiinodiquinolines with var-

ious O-, S-, Se-, N- and C-nucleophiles have brought very convenient

and efﬁcient synthesis of 2,3^ꢀ-, 3,3^ꢀ- and 3,4^ꢀ-diquinolinyl sulﬁdes.¹³Very

recently we found 2,2^ꢀ-disubstituted -3,3^ꢀ-diquinolinyl sulﬁdes to be ex-

cellent substrates for the synthesis of heteropentacenes.¹⁴

In continuation we would like to report the synthesis of the

title compounds by the 1,4-dithiin ring opening reactions in

Received October 12, 2004; accepted October 26, 2004.

LXXXIII in the series of Azinyl Sulﬁdes.

Address correspondence to Krystian Pluta, The Medical University of Silesia,

Department of Organic Chemistry, Jagiellon´ska 4, Sosnowiec 41-200, Poland. E-mail:

pluta@slam.katowice.pl

2457

2458

K. Pluta

1,4-dithiinodiquinoline (common name: isothioquinanthrene) 1 with

selected O-nucleophiles and further transformations to sulﬁdes pos-

sessing one or two 4(1H)-quinolone units.

RESULTS AND DISCUSSION

The dithiin ring opening reactions in isothioquinanthrene 1 with

sodium methanolate and sodium hydroxide led, after the methy-

lation stage, to two isomeric 3,3^ꢀ-diquinolinyl sulﬁdes (2a and 3a,

Scheme 1).^13dBoth sulﬁdes showed unexpected ¹H NMR spectroscopic

effects (a signiﬁcant shielding and deshielding of some protons) being

a result of the conformations with donor–acceptor interactions of the

heteroatoms as concluded from their X-ray analysis.^15,16

SCHEME 1

The unexpected sulﬁde 3a, possessing one 4(1H)-quinolone unit,

prompted us to further study the reactions of isothioquinanthrene 1

with O-nucleophiles such as sodium and potassium hydroxides and

sodium alkoxides.

The 1,4-dithiin ring opening reactions in isothioquinoline 1 with O-

nucleophiles were carried out in DMSO at 70^◦C. The progress of the

reaction was followed by observation of a color of the reaction mixture

(a change of yellow to deep red) and dissolution of a suspension of isoth-

ioquinanthrene 1 into a solution during the course of the reaction (in the

end of this stage the reaction mixture became a transparent solution).

The reaction mixture was poured into a threefold volume of 15% aque-

ous sodium hydroxide solution and was alkylated with alkyl halides to

form the ﬁnal product. All of the discussed reactions proceeded with a

cleavage of only one C_quinolinylS bond.

Substituted 3,3^ꢀ-Diquinolinyl Sulﬁdes

2459

The reaction of isothioquinanthrene 1 with powdered sodium

hydroxide led to a disodium salt of 4-hydroxy-4^ꢀ-mercapto-3,3^ꢀ-

diquinolinyl sulﬁde 4 as a primary product, which was soluble in DMSO.

The DMSO-aqueous NaOH solution of sulﬁde 4, when alkylated with

methyl iodide, gave the ﬁnal product as an insoluble solid. The ﬁnal

product was identiﬁed as 1-methyl-1,4-dihydro-4-oxo-4^ꢀ-methylthio-

3,3^ꢀ-diquinolinyl sulﬁde 3a. Direct acidiﬁcation of the salt 4 with

diluted hydrochloric acid to pH = 7 to obtain free 1,4-dihydro-4-oxo-

4^ꢀ-mercapto-3,3^ꢀ-diquinolinyl sulﬁde 5 was unsuccessful because of a

tendency of intramolecular cyclization to form back to isothioquinan-

threne 1. The unexpected structure of sulﬁde 3a was the result of the

alkylation of sodium salt 4 possessing three nucleophilic centers, i.e.,

the oxygen, nitrogen, and sulfur atoms (Scheme 2).

SCHEME 2

Since the most nucleophilic center is at the sulfur atom the alkyla-

tion stage with only 1.3 equivalents of alkylating agents (methyl iodide,

ethyl iodide, and benzyl chloride) proceeded mainly as an S-alkylation.

Such a product can be isolated after acidiﬁcation of the reaction mix-

ture with diluted hydrochloric acid to pH = 9 as sulﬁdes 7a–7c, pos-

sessing one quinolinyl and one 4(1H)-quinolonyl units. Only an excess

of the alkylating agent enables further alkylation of the quinolonyl

unit to form the N-alkyl derivatives 3a–3f. When 2.6 equivalents of the

alkylating agent (methyl iodide) were used, both sulﬁde 3a (49%) and

sulﬁde 7a (34%) were obtained. Only 4 equivalents of the alkylating

2460

K. Pluta

TABLE I Reactions of Isothioquinanthrene 1 With Selected Oxygen

Nucleophiles in DMSO at 70^◦C

Alkylating Agent

(Equivalents)

No. Nucleophile

Products (%) R, R^ꢀ

1

2

3

4

5

6

7

8

EtONa

PhCH₂ONa

NaOH

EtI (1.3)

2c R = R^ꢀ= Et (87)

MeI (1.3)

PhCH₂Cl (1.3)

MeI (1.3)

MeI (4)

MeI (2.6)

EtI (1.3)

2d R = PhCH₂, R^ꢀ= Me (92)

2e R = R^ꢀ= PhCH₂(90)

7a R = H, R^ꢀ= Me (88)

3a R = R^ꢀ= Me (85)

3a R = R^ꢀ= Me (49), 7a R = H, R^ꢀ= Me (34)

7b R = H, R^ꢀ= Et (85)

EtI (4)

3e R = R^ꢀ= Et (76)

9

10

11

PhCH₂Cl (1.3)

PhCH₂Cl (4)

MeI (4)

7c R = H, R^ꢀ= PhCH₂(89)

3f R = R^ꢀ= PhCH₂(87)

KOH

3a R = R^ꢀ= Me (11), 7a R = H, R^ꢀ= Me (11),

8 R = R^ꢀ= Me (63)

agents gave sulﬁdes 3a, 3e, and 3f in good yields (76–87%; Table I,

Scheme 3).

SCHEME 3

In the literature one can ﬁnd procedures of alkylation of 4(1H)-

quinolones but they need a boiling ethanolic solution of sodium or potas-

sium hydroxides,^17,18anhydrous aprotic solvent and sodium hydride,¹⁹

trialkyl phosphate,²⁰or a ten-fold amount of alkylating agent.¹⁸Our

procedure of alkylation in the mixture of DMSO-15% aqueous NaOH

(1:3) at room temperature, which was widely veriﬁed during synthesis of

quinolinyl sulﬁdes from quinolinethiolates and alkylating agents (alkyl

halides, dialkyl sulfates and alkylene ditosylates),^{13a,13c−13f,21}is very

simple and efﬁcient and enables direct observation of the alkylation

progress and direct separation of insoluble alkylated products from a

soluble acidic substrate by ﬁltration.

Substituted 3,3^ꢀ-Diquinolinyl Sulﬁdes

2461

TABLE II Alkylations of Sulﬁdes 7 With Alkylating

Agents in the DMSO-15% NaOH Mixture

Alkylating Agent

(Equivalents)

No. Sulﬁde

Products (%) R, R^ꢀ

1

2

3

4

5

6

7a

7b

7c

MeI (3)

EtI (3)

PhCH₂Cl (3)

MeI (3)

EtI (3)

3a R = R^ꢀ= Me (88)

3b R = Et, R^ꢀ= Me (79)

3c R = PhCH₂, R^ꢀ= Me (86)

3d R = Me, R^ꢀ= Et (87)

3e R = R^ꢀ= Et (76)

PhCH₂Cl (3)

3f R = R^ꢀ= PhCH₂(89)

The isolated sulﬁdes 7a–7c after acidiﬁcation can be further alky-

lated in the mixture of DMSO-15% aqueous NaOH (1:3) with the same

or another alkylating agent. This method enables us to obtain substi-

tuted quinolonyl-quinolinyl sulﬁdes 3 with the same (3a, 3e, and 3f)

or different alkyl groups R and R^ꢀ(3b–3d) attached to the sulfur and

nitrogen atoms in good yields (76–89%) (Tables I and II).

Because of hydroscopic properties of sodium hydroxide we tried to

use the less hydroscopic potassium hydroxide in the dithiin ring open-

ing reaction. Reaction of isothioquinanthrene 1 with potassium hy-

droxide in DMSO proceeded very smoothly and led unexpectedly, after

methylation, to 4,4^ꢀ-dimethylthio-3,3^ꢀ-diquinolinyl sulﬁde 8 (63%) to-

gether with sulﬁde 3a (11%) and sulﬁde 7a (11%; Scheme 4).

SCHEME 4

Since the reactions of isothioquinanthrene 1 with sodium alkoxides

run faster than with sodium hydroxide,^13dwe examined reactions with

sodium ethoxide and sodium benzyloxide in DMSO at 70^◦C. After alky-

lation with alkyl halides (ethyl iodide and benzyl chloride), 4-alkoxy-4^ꢀ-

alkylthio-3,3^ꢀ-diquinolinyl sulﬁdes 2c–2e were isolated in 87–92% yield

(Scheme 5).

2462

K. Pluta

SCHEME 5

We reported the thermal O–N migration of the methyl group in 4-

methoxy-3-methylthioquinoline to give 1-methyl-3-methylthio-4(1H)-

quinolone in high yield²²and this result prompted us to examine 4-

alkoxy-4^ꢀ-methylthio-3,3^ꢀ-diquinolinyl sulﬁdes 2a–2e, possessing the

methoxy, ethoxy, and benzyloxy groups. These sulﬁdes heated at 200^◦C

in or without a solvent and underwent the thermal rearrangement to

give the products of the alkyl group migration, i.e., 1-alkyl-quinolonyl-

quinolinyl sulﬁdes 3a–3c, 3e, and 3d (alkyl = methyl, ethyl, and benzyl)

in a 55–90% yield (Table III).

This rearrangement is the evidence for the 4-alkoxyquinoline struc-

ture of sulﬁdes 2 and 1-alkyl-4(1H)-quinolone structure of sulﬁdes 3.

Structures of isomeric sulﬁdes 2a and 3a were determined on the basis

1

of the H NMR experiments (COSY, HETCOR, and NOE) and ﬁnally

conﬁrmed by the X-ray analysis of their monocrystals.^15,16We observed

a characteristic downﬁeld shift of the H-5 proton signal in sulﬁdes 2 and

3 but we observed only an upﬁeld shift of the H-8 proton in sulﬁdes 3

in comparison with the appropriate signals in unsubstituted quinoline.

TABLE III The Thermal Rearrangement of Sulﬁde 2 to

Sulﬁde 3. EEDG = Monoethyl Ether of Diethylene Glycol

No.

Sulﬁde R, R^ꢀ

Conditions (^◦C/min.)

Products (%)

1

2

3

4

5

6

2a R = R^ꢀ= Me

200/60, in EEDG

200/30 neat

3a (61)

3a (90)

3b (55)

3c (58)

3e (60)

3f (56)

2a R = R^ꢀ= Me

2b R = Et, R^ꢀ= Me

2c R = PhCH₂, R^ꢀ= Me

2d R = R^ꢀ= Et

2e R = R^ꢀ= PhCH₂

Substituted 3,3^ꢀ-Diquinolinyl Sulﬁdes

2463

The shielding and deshielding of these protons are the results of the peri

interactions between the hydrogen atoms and the 4-and 1-substituents.

We found the alkoxy groups in 4-alkoxy-4^ꢀ-alkylthio-3,3^ꢀ-diquinolinyl

sulﬁdes 2a–2e to be susceptible to hydrolysis in acidic conditions. Heat-

ing these sulﬁdes in the hydrochloric acid-ethanol mixture (1:1) for 0.5 h

led directly to hydrochlorides of N-unsubstituted quinolonyl-quinolinyl

sulﬁdes 7a–7c. When the heating of sulﬁdes 2a–2c was carried for

48 h, not only the hydrolysis of the alkoxy group but also the hydrol-

ysis of the alkylthio group was observed followed by an evolution of

alkanethiol. After cooling we isolated hydrochloride of diquinolonyl sul-

ﬁde (hydrochloride of 3,3^ꢀ-bis(1,4-dihydro-4-oxoquinolinyl) sulﬁde) 8²³

in a high yield (Table IV, Scheme 5). To avoid the emission of odor-

ous volatile alkanethiol to the atmosphere, we trapped this thiol in

an aqueous sodium hydroxide solution and oxidized it with potassium

permangante.

The hydrochloride function in hydrochlorides of sulﬁdes 7a–7c and 8

can be easily withdrawn to give free sulﬁdes 7a–7c and 8 by dissolving

in the mixture of DMSO-15% aqueous NaOH (1:3) and precipitating

with hydrochloric acid. As expected, sulﬁdes 7a and 7b underwent the

reaction with the hydrochloric acid-ethanol mixture (1:1) for 48 h to

give sulﬁde 8 in an 87% and 94% yield (Table IV).

It is worth noting that N-unsubstituted diquinolonyl sulﬁde 8 is

an excellent initial compound in the synthesis of various pentacyclic

heterocyclodiquinolines.^21,23−25Sulﬁde 8 as a 4(1H)-quinolone deriva-

tive can be alkylated with selected alkyl halides. Alkylation in the

same conditions as described above but with more equivalents of alkyl

halides and longer reaction time proceeded as the N-alkylation, giving

TABLE IV Reactions of Sulﬁdes 2, 3a, and 7 With

the Hydrochloric Acid-Ethanol Mixture

No.

Sulﬁde R, R^ꢀ

Conditions (h)

Products (%)

1

2

3

4

5

6

7

8

2a R = R^ꢀ= Me

0.5

48

7a (91)

7a (87)

7a (80)

7b (88)

7c (77)

8 (94)

8 (91)

8 (94)

2b R = Et, R^ꢀ= Me

2c R = PhCH₂, R^ꢀ= Me

2d R = R^ꢀ= Et

2e R = R^ꢀ= PhCH₂

2a R = R^ꢀ= Me

2b R = Et, R^ꢀ= Me

2c R = PhCH₂, R^ꢀ= Me

2d R = R^ꢀ= Et

9

10

11

12

7a R = H, R^ꢀ= Me

7b R = H, R^ꢀ= Et

3a R = R^ꢀ= Me

48

8 (87)

10 (87)

2464

K. Pluta

SCHEME 6

symmetrical N,N-disubstituted diquinolonyl sulﬁdes (bis(1-alkyl-1,4-

dihydro-4-oxo-3-quinolinyl) sulﬁdes) 9a–9e, possessing two identical

alkyl groups, in good yield (Table II, Scheme 6). In order to obtain un-

symmetrical N,N-disubstituted diquinolonyl sulﬁdes (possessing two

different alkyl groups), we carried out consecutive alkylation with two

different alkyl halides in the mixture of DMSO-15% aqueous NaOH.

Sulﬁde 8 was ﬁrst alkylated with 1.5 equivalents of methyl iodide to

give the monomethyl derivative, i.e., 1-methylbis(1,4-dihydro-4-oxo-3-

quinolinyl) sulﬁde 10 as the main product, which was soluble in the

reaction mixture, and a small amount of the dimethyl derivative, i.e.,

sulﬁde 9a (11%, insoluble, isolated by ﬁltration). Sulﬁde 10 next was

alkylated with 3 equivalents of benzyl chloride to give the ﬁnal product

as an insoluble compound—1-methyl-1^ꢀ-benzylbis(1,4-dihydro-4-oxo-3-

quinolinyl) sulﬁde 9f in a good yield (71%, Table V).

An alternative way to obtain sulﬁde 9f is based on the observation

of a behavior of the substituents in sulﬁdes 2 and 3 during the reaction

with the hydrochloric acid-ethanol mixture. Whereas the alkoxy and

alkylthio groups in position 4 are susceptible to hydrolysis (a cleavage

of the C O and C S bonds) during the reaction, the alkyl group in

position 1 is quite stable (a stability of the C N bond). The reaction of

Substituted 3,3^ꢀ-Diquinolinyl Sulﬁdes

2465

TABLE V Alkylations of Sulﬁdes 8 and 10 With Alkylating Agents

in the DMSO-15% NaOH Mixture

Alkylating Agent

No. Sulﬁde (Equivalents)

Conditions

(^◦C/h)

Products (%) R R^ꢀ

1

2

3

4

5

6

7

8

MeI (6)

EtI (6)

PrI (6)

AllBr (6)

PhCH₂Cl (6)

MeI (1.5), PhCH₂Cl (3)

20/24

60/24

20/24

20/48

9a R = R^ꢀ= Me (86)

9b R = R^ꢀ= Et (22)

9b R = R^ꢀ= Et (59)

9c R = R^ꢀ= Pr (55)

9d R = R^ꢀ= All (76)

9e R = R^ꢀ= PhCH₂(86)

9a (11), 9fR = Me, R^ꢀ=

PhCH₂(71)

8

9

10

8

10

CH₂I₂(3)

BrCH₂CH₂CH₂Br (3)

PhCH₂Cl (3)

60/24

20/24

11 (54)

9d R = R^ꢀ= All (40)

9f R = Me, R^ꢀ= PhCH₂(87)

sulﬁde 3a with the hydrochloric acid-ethanol mixture for 48 h led to

sulﬁde 10 (in an 87% yield), which when alkylated in the DMSO-NaOH

mixture with benzyl chloride gave sulﬁde 9f in a good yield (87% yield,

Scheme 6).

Sulﬁde 8 as a two-functional substrate can be alkylated with two-

functional alkylating agents to form crown ethers containing two or

four 4-quinolone moieties, similar to those crown thioethers contain-

ing two or four quinoline moieties obtained from dithiinodiquinolines.²¹

The reaction of sulﬁde 8 with diiodomethane in the DMSO-NaOH mix-

ture at 60^◦C for 24 h led to a product of intramolecular bisalkylation

(the substrate/methylene group ratio 1:1, m/z = 332 (M, 100% in a

54% yield. Steric requirements in sulﬁde 8 excluded an intramolec-

1

ular N,N-bisalkylation to form an N-CH₂-N fragment. The H NMR

spectrum analysis revealed an absence of the upﬁeld shift of the H-8

proton (δ = 8.04 ppm), which was typical for 1-alkyl-4(1H)-quinolones

and a weaker downﬁeld shift of the H-5 proton (δ = 8.28 ppm) instead

of the expected values (δ = 7.36–7.41 ppm and δ = 8.41–8.43 ppm, re-

spectively, in compounds 9a–9d). The methylene protons are strongly

shifted downﬁeld (δ = 7.10 ppm), even more than for the ArOCH₂OAr

region (δ = 6.1–6.7 ppm) and much more than in the ArNCH₂NAr region

(δ = 4–4.5 ppm).²⁶More evidence came from the ¹³C NMR spectrum. We

observed the C₄carbon at 158.90 ppm, which is close to the carbon signal

of C₄-OCH₃at 162.7 ppm²⁷in 4,4^ꢀ-dimethoxy-3,3^ꢀ-diquinolinyl sulﬁde

12 (Scheme 7), but is unlike the carbon C₄O signal at 177.7 ppm²⁸in

sulﬁde 9a. Also the C₈carbon signal at 130.73 ppm is similar to the

appropriate signal at 130.2 ppm²⁷in sulﬁde 12 but unlike the signal

1

in sulﬁde 9a (116.2 ppm).²⁸The H and ¹³C NMR effects suggest the

2466

K. Pluta

SCHEME 7

formation of an O-CH₂-O fragment with some steric strains and the

structure of compound 11 as dioxathia-8-crown-3 (Scheme 6). Reaction

of sulﬁde 8 with 1,2-dibromoethane led to a polymeric product and with

1,3-dibromopropane led mainly to a product of subsequent elimination

of hydrobromic acid instead of further alkylation, i.e., sulﬁde 9d.

In conclusion we report a simple method of synthesis of selected

substituted diquinolinyl 2, quinolinyl-quinolonyl 3, diquinolonyl sul-

ﬁdes 9, and dioxathia-8-crown-3 11 via 1,4-dithiin ring opening in 1,4-

dithiinodiquinoline 1 followed by the S-, O-, and N-alkylation; the O-N

alkyl migration; and the transformation of the alkoxy and alkylthio

substituents.

EXPERIMENTAL

Melting points were determined in open capillary tubes on a Boetius

1

melting point apparatus and are uncorrected. The H and ¹³C NMR

spectra were recorded on a Varian Unity-Inova-300 spectrometer at

300 MHz and 75 MHz in deuteriochloroform and dimethyl sulphoxide-

d₆with tetramethylsilane as the internal standard. Electron impact

mass spectra (EI MS) were run on a LKB 9000S at 70 eV and a chem-

ical ionization mass spectrum (CI MS) was run on a Finnigan MAT 95

spectrometer.

Isothioquinanthrene (1) was obtained from thioquinanthrene (the

exhaustive sulfuration product of quinoline with elemental sulfur)²⁹

via ring opening–ring closure reactions.³⁰Sulﬁdes 2a and 2b were ob-

tained from reactions of isothioquinanthrene 1 with sodium alkoxides

followed by the S-alkylation with alkyl halides according to the de-

scribed procedure.^13d

Reactions of Isothioquinanthrene 1 with Sodium Alkoholates

To a suspension of isothioquinanthrene 1 (0.32 g, 1 mmol) in 10 mL

of dry DMSO at 70^◦C, sodium ethoxide (0.20 g, 3 mmol) or sodium

Substituted 3,3^ꢀ-Diquinolinyl Sulﬁdes

2467

benzyloxide (0.39 g, 3 mmol) was added. The mixture was stirred for

30 min, then cooled and poured into 30 mL of 15% aqueous sodium

hydroxide. Residual dithiin 1 was ﬁltered and the ﬁltrate was stirred

with alkyl halides (methyl iodide, ethyl iodide, and benzyl chloride, 1.3

mmols, Table I). The resulting solid was collected by ﬁltration, washed

with water, and air-dried. The crude product was puriﬁed by column

chromatography (silica gel 60, chloroform) to give sulﬁdes 2c–2e.

4-Ethoxy-4^ꢀ-ethylthio-3,3^ꢀ-diquinolinyl Sulﬁde 2c, Viscous Oil

¹H NMR (CDCl₃) δ 1.31 (t, 3H, J = 7.4 Hz, SCH₂CH₃), 1.44 (t, 3H,

J = 7.4 Hz, OCH₂CH₃), 3.09 (q, 2H, J = 7.4 Hz, SCH₂), 4.46 (q, 2H, J =

7.4 Hz, OCH₂), 7.61, 7.65, 7.67 and 7.78 (4 m, 4H, H-6, H-6^ꢀ, H-7 and

H-7^ꢀ), 8.01 and 8.12 (2dd, 2H, H-8 and H-8^ꢀ), 8.20 and 8.55 (2dd, 2H,

H-5 and H-5^ꢀ), 8.28 and 8.85 (2s, 2H, H-2 and H-2^ꢀ). EI MS (70 eV) m/z:

392 (M, 100), 363 (M-C₂H₅,30.0), 302 (M-(C₂H₅)₂S, 53.7). Anal. Calcd.

for C₂₂H₂₀N₂OS₂(392.53): C,67.32; H, 5.14; N, 7.14. Found: C, 67.22;

H, 5.19; N, 7.01.

4-Benzyloxy-4^ꢀ-methylthio-3,3^ꢀ-diquinolinyl Sulﬁde 2d,

Viscous Oil

¹H NMR (CDCl₃) δ: 2.50 (s, 3H, SCH₃), 5.43 (s, 2H, OCH₂) 7.27 and

7.35 (2 m, 5H, C₆H₅), 7.56, 7.64, 7.68 and 7.77 (4 m, 4H, H-6, H-6^ꢀ, H-7

and H-7^ꢀ), 8.02 and 8.14 (2dd, 2H, H-8 and H-8^ꢀ), 8.12 and 8.50 (2dd,

2H, H-5 and H-5^ꢀ), 8.33 and 8.87 (2s, 2H, H-2 and H-2^ꢀ). CI MS (70 eV)

m/z: 441 (M+1, 100), 393 (M-CH₃S, 24.1). Anal. Calcd. for C₂₆H₂₀N₂OS₂

(440.57): C, 70.88; H, 4.58; N,6.36: Found: C, 70.52; H, 4.62; N, 6.11.

4-Benzyloxy-4^ꢀ-benzylthio-3,3^ꢀ-diquinolinyl Sulﬁde 2e,

Viscous Oil

¹H NMR (CDCl₃) δ: 4.14 (s, 2H, SCH₂), 5.39 (s, 2H, OCH₂), 7.08–7.38

(m, 10H, 2C₆H₅), 7.56, 7.57, 7.65 and 7.77 (4 m, 4H, H-6, H-6^ꢀ, H-7 and

H-7^ꢀ), 7.99 and 8.13 (2dd, 2H, H-8 and H-8^ꢀ), 8.12 and 8.40 (2dd, 2H,

H-5 and H-5^ꢀ), 8.26 and 8.72 (2s, 2H, H-2 and H-2^ꢀ). CI MS (70 eV) m/z:

517 (M+1, 4.0), 426 (M+1-C₆H₅CH₂, 22.9) 410 (M+1-C₆H₅CH₂O, 19.1),

358 (M+I-C₉H₅NS, 10.2), 319 (M+1-(C₆H₅CH₂)₂O, 71.3), 303 (M+1-

(C₆H₅CH₂)₂S, 100). Anal. Calcd. for C₃₂H₂₄N₂OS₂(516.67): C, 74.39;

H, 4.68; N, 5.42. Found: C, 74.19; H, 4.58; N, 5.22.

Reactions of Isothioquinanthrene 1 with Sodium Hydroxide

To a suspension of isothioquinanthrene 1 (0.32 g, 1 mmol) in 10 mL

of dry DMSO at 70^◦C, powdered sodium hydroxide (0.12 g, 3 mmol)

was added. The mixture was stirred for 60 min, cooled, and poured into

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30 mL of 15% aqueous sodium hydroxide. Residual dithiin 1 was ﬁltered

and the ﬁltrate was stirred with alkyl halides (methyl iodide, ethyl io-

dide, and benzyl chloride, 2.6 and 4 equivalents at once, 1.3 equivalents

in 1 mL of DMSO solution added drop by drop during 1 h, Table I). The

resulting solid was collected by ﬁltration, washed with water, and air-

dried. The crude product was puriﬁed by column chromatography (silica

gel 60, chloroform) to give sulﬁdes 3a, 3e, and 3f (Table I). The ﬁltrate

was acidiﬁed with diluted hydrochloric acid to pH = 9 and the resulting

solid was collected by ﬁltration, washed with water, and air-dried to

give sulﬁdes 7a–7c.

1-Methyl-1,4-dihydro-4-oxo-4^ꢀ-methylthio-3,3^ꢀ-diquinolinyl sulﬁde

3a, mp 252–253^◦C, lit.^13dm.p. 252–253^◦C. ¹H NMR (CDCl₃) δ: 2.59 (s,

3H, SCH₃), 3.88 (s, 3H, NCH₃), 7.47, 7.60 and 7.74 (3m, 5H, H-6, H-6^ꢀ,

H-7, H-7^ꢀand H-8), 7.98 (dd, 1H, H-8^ꢀ), 8.17 and 8.42 (2s, 2H, H-2 and

H-2^ꢀ), 8.45 and 8.50 (2dd, 2H, H-5 and H-5^ꢀ).

1-Ethyl-1,4-dihydro-4-oxo-4^ꢀ-ethylthio-3,3^ꢀ-diquinolinyl Sulﬁde

3e, m.p. 155–156^◦C

¹H NMR (CDCl₃) δ: 1.32 (t, 3H, J = 7.3 Hz, SCH₂CH₃), 1.56 (t, 3H,

J = 7.3 Hz, NCH₂CH₃), 3.13 (q, 2H, J = 7.3 Hz, SCH₂), 4.26 (q, 2H,

J = 7.3 Hz, NCH₂), 7.44, 7.58, 7.61 and 7.73 (4m, 4H, H-6, H-6^ꢀ, H-7

and H-7^ꢀ), 7.51 and 7.97 (2dd, 2H, H-8 and H-8^ꢀ), 8.18 and 8.43 (2s, 2H,

H-2 and H-2^ꢀ), 8.49 and 8.53 (2dd, 2H, H-5 and H-5^ꢀ). EI MS (70 eV)

m/z: 392 (M, 13.9), 331 (M-C₂H₅S, 100), 302 (M-(C₂H₅)₂S, 17.4). Anal.

Calcd. for C₂₂H₂₀N₂OS₂(392.53): C, 67.32; H, 5.14; N, 7.14. Found: C,

67.18; H, 5.20; N, 7.03.

1-Benzyl-1,4-dihydro-4-oxo-4^ꢀ-benzylthio-3,3^ꢀ-diquinolinyl

Sulﬁde 3f, m.p. 146–147^◦C

¹H NMR (CDCl₃) δ: 4.29 (s, 2H, SCH₂), 5.40 (s, 2H, NCH₂), 7.14–

7.62 (m, 15H, 2C₆H₅, H-6; H-6^ꢀ, H-7, H-7^ꢀand H-8), 7.95 (dd, 1H, H-

8^ꢀ), 8.20 and 8.50 (2s, 2H, H-2 and H-2^ꢀ), 8.33 and 8.48 (2dd, 2H, H-5

and H-5^ꢀ). CI MS (70 eV) m/z: 517 (M+1, 4.0), 426 (M+1-C₆H₅CH₂,

7.1) 410 (M+1-C₆H₅CH₂O, 13.5), 358 (M+1-C₉H₅NS, 100), 319 (M+1-

(C₆H₅CH₂)₂O, 65.7), 303 (M+1-(C₆H₅CH₂)₂S, 22.1). Anal. Calcd. for

C₃₂H₂₄N₂OS₂(516.67): C, 74.39; H, 4.68; N, 5.42. Found: C, 74.30; H,

4.62; N, 5.26.

1,4-Dihydro-4-oxo-4^ꢀ-methylthio-3,3^ꢀ-diquinolinyl Sulﬁde 7a,

m.p. 267–268^◦C, lit.³¹m.p. 268–269^◦C.

1,4-Dihydro-4-oxo-4^ꢀ-ethylthio-3,3^ꢀ-diquinolinyl sulﬁde 7b, m.p.

262–263^◦C, lit.³¹m.p. 263–264^◦C.

Substituted 3,3^ꢀ-Diquinolinyl Sulﬁdes

2469

1,4-Dihydro-4-oxo-4^ꢀ-benzylthio-3,3^ꢀ-diquinolinyl sulﬁde 7c, m.p.

215–216^◦C.

¹H NMR (DMSO-d₆) δ: 4.42 (s, 2H, SCH₂), 7.22 and 7.32 (2m, 5H,

C₆H₅), 7.48, 7.59, 7.68 and 7.76 (4m, 4H, H-6, H-6^ꢀ, H-7 and H-7^ꢀ), 7.78

and 7.94 (2dd, 2H, H-8 and H-8^ꢀ), 8.21 and 8.30 (2dd, 2H, H-5 and H-

5^ꢀ), 8.36 and 8.63 (2s, 2H, H-2 and H-2^ꢀ), 12.2 (broad, 1H, NH). CI MS

(70 eV) m/z: 427 (M+1, 3.4), 319 (M+1-C₆H₅CH₂OH, 19.2), 303 (M+1-

C₆H₅CH₂SH, 100). Anal. Calcd. for C₂₅H₁₈N₂OS₂(426.55): C, 70.40; H,

4.25; N, 6.57. Found: C, 70.19; H, 4.35; N, 6.32.

Reactions of Isothioquinanthrene 1 with Potassium Hydroxide

To a suspension of isothioquinanthrene 1 (0.32 g, 1 mmol) in 10 mL

of dry DMSO at 70^◦C, pellets of potassium hydroxide (0.17 g, 3 mmol)

were added. The mixture was stirred for 20 min, cooled, and poured into

30 mL of 15% aqueous sodium hydroxide. Residual dithiin 1 was ﬁltered

off and the ﬁltrate was stirred with methyl iodide (0.25 mL, 4 mmols).

The resulting solid was collected by ﬁltration, washed with water, and

air-dried. The crude product was puriﬁed by column chromatography

(silica gel 60, chloroform) to give 4,4^ꢀ-dimethylthio-3,3^ꢀ-diquinolinyl sul-

ﬁde 8 (0.24 g, 63%, m.p. 142–143^◦C, lit.^13am.p. 142–143^◦C) and sulﬁde

3a (0.04 g, 11%). The ﬁltrate was acidiﬁed with diluted hydrochloric acid

to pH = 9 and the resulting solid was collected by ﬁltration, washed with

water, and air-dried to give sulﬁdes 7a (0.04 g, 11%, m.p. 267–268^◦C,

lit.³¹m.p. 268–269^◦C).

Alkylations of Sulﬁdes 7 with Alkylating Agents

To a stirred solution of sulﬁde 7a–7c (1 mmol) in the mixture of 2 mL

of DMSO and 6 mL of 15% aqueous sodium hydroxide at 20^◦C, an alkyl

halide (methyl iodide, ethyl iodide, and benzyl chloride, 3.6 mmol, Ta-

ble II) was added. The mixture was stirred for 24 h. The resulting solid

was collected by ﬁltration, washed with water, and air-dried. The crude

product was puriﬁed by column chromatography (silica gel 60, chloro-

form, chloroform-ethanol) to give sulﬁde 3b–3d (Table II).

1-Ethyl-1,4-dihydro-4-oxo-4^ꢀ-methylthio-3,3^ꢀ-diquinolinyl

Sulﬁde 3b, m.p. 149–150^◦C

¹H NMR (CDCl₃) δ: 1.56 (t, 3H, J = 7.3 Hz, CH₃), 2.60 (s, 3H, SCH₃),

4.27 (t, 2H, J = 7.3 Hz, NCH₂), 7.44, 7.59, 7.62 and 7.73 (4m, 4H, H-6,

H-6^ꢀ, H-7 and H-7^ꢀ), 7.50 and 7.97 (2dd, 2H, H-8 and H-8^ꢀ), 8.20 and

8.44 (2s, 2H, H-2 and H-2^ꢀ), 8.48 and 8.51 (2dd, 2H, H-5 and H-5^ꢀ). EI

MS (70 eV) m/z: 378 (M, 5.6), 363 (M-CH₃, 5.6), 331 (M-CH₃S, 100), 302

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K. Pluta

(M-C₂H₅SCH₃, 15.3). Anal. Calcd. for C₂₁H₁₈N₂OS₂(378.50): C, 66.64;

H, 4.79; N, 7.40. Found: C, 66.49; H, 4.81; N, 7.24.

1-Benzyl-1,4-dihydro-4-oxo-4^ꢀ-methylthio-3,3^ꢀ-diquinolinyl

Sulﬁde 3c, m.p. 201–202^◦C

¹H NMR (CDCl₃) δ: 2.60 (s, 3H, SCH₃), 5.41 (s, 2H, NCH₂) 7.20, 7.37

and 7.60 (3m, 10H, C₆H₅, H-6, H-6^ꢀ, H-7, H-7^ꢀand H-8), 7.99 (dd, 1H,

H-8^ꢀ), 8.28 and 8.52 (2s, 2H, H-2 and H-2^ꢀ), 8.47 and 8.52 (2dd, 2H, H-5

and H-5^ꢀ). CI MS (70 eV) m/z: 441 (M+1, 100), 393 (M+1-CH₃S, 18.2),

303 (M+1-C₆H₅CH₂SCH₃, 1.8). Anal. Calcd. for C₂₆H₂₀N₂OS₂(440.67):

C, 70.88; H, 4.58; N, 6.36. Found: C, 70.59; H, 4.62; N, 6.22.

1-Methyl-1,4-dihydro-4-oxo-4^ꢀ-ethylthio-3,3^ꢀ-diquinolinyl

Sulﬁde 3d, m.p. 225–226^◦C

¹H NMR (CDCl₃) δ: 1.32 (t, 3H, J = 7.3 Hz, CH₃), 3.13 (t, 2H, J =

7.3 Hz, SCH₂), 3.87 (s, 3H, NCH₃), 7.46, 7.58, 7.60 and 7.74 (4m, 4H,

H-6, H-6^ꢀ, H-7 and H-7^ꢀ), 7.45 and 7.96 (2dd, 2H, H-8 and H-8^ꢀ), 8.14

and 8.42 (2s, 2H, H-2 and H-2^ꢀ), 8.47 and 8.52 (2dd, 2H, H-5 and H-

5^ꢀ). EI MS (70 eV) m/z: 378 (M, 7.5), 349 (M-C₂H₅, 3.6), 317 (M-C₂H₅S,

100), 302 (M-C₂H₅SCH₃, 5.5). Anal. Calcd. for C₂₁H₁₈N₂OS₂(378.50):

C, 66.64; H, 4.79; N, 7.40. Found: C, 66.23; H, 4.84; N, 7.19.

The Thermal Rearrangement of Sulﬁdes 2 to Sulﬁdes 3

(a) Sulﬁde 2a–2e (0.5 mmol) was heated in a test tube at 200^◦C for 30

min. After cooling the rearrangement product was extracted with

chloroform and puriﬁed by column chromatography (silica gel 60,

chloroform, chloroform-ethanol) to give sulﬁde 3a–3c, 3e, and 3f

(Table III).

(b) Sulﬁde 2a (0.18 g, 0.5 mmol) was heated in 1 mL of boiling mo-

noethyl ether of diethylene glycol for 1 h. After cooling the solution

was poured into 5 mL of water and the resulting solid was collected

by ﬁltration, washed with water, and air-dried. The crude product

was puriﬁed by column chromatography (silica gel 60, chloroform,

chloroform-ethanol) to give sulﬁde 3a (0.11 g, 61%).

Reactions of Sulﬁdes 2 and 3 with the Hydrochloric

Acid-Ethanol Mixture

(a) A solution of sulﬁde, 2a–2e (1 mmol) in 3 mL of the mixture of

concentrated hydrochloric acid-ethanol (1:1) was reﬂuxed for 30

min. After cooling the resulting solid was collected by ﬁltration,

washed with ethanol, and air-dried. The product was identiﬁed

Substituted 3,3^ꢀ-Diquinolinyl Sulﬁdes

2471

as hydrochloride of sulﬁde 7a–7c (m.p. 187–188^◦C, Belstein test,

elementary analysis for hydrochloride of sulﬁde 7a: calcd. for

C₁₉H₁₄N₂OS₂· 2HCl · H₂O (441.39) C, 51.70; H, 4.11; N, 6.35; Cl,

16.06; S, 14.53. Found: C, 51.63; H, 3.93; N, 6.34; Cl, 16.06; S, 14.31).

Neutral sulﬁdes 7a–7c were obtained from their hydrochlorides by

dissolving in 6 mL of the mixture DMSO-15% aqueous sodium hy-

droxide (1:3) and precipitating with 10% hydrochloric acid to pH =

9. The resulting solid was collected by ﬁltration, washed with water,

and air-dried (Table IV).

(b) A solution of sulﬁde, 2, 3a, or 7 (1 mmol) in 10 mL of the mixture of

concentrated hydrochloric acid-ethanol (1:1) was reﬂuxed for 48 h.

The volatile odorous alkanethiol leaking out of the condenser was

trapped in a container with an aqueous solution of potassium per-

manganate and sodium hydroxide. After cooling the resulting solid

was collected by ﬁltration, washed with ethanol, and air-dried. The

product was identiﬁed as hydrochloride of sulﬁde 8 (Belstein test,

1

m.p. >300^◦C, lit.²³m.p. >300^◦C, H NMR spectrum as described

in ref.²³). Neutral sulﬁde 8 was obtained from its hydrochloride by

dissolving in 2 mL of the mixture DMSO-15% aqueous sodium hy-

droxide (1:3) and precipitating with 10% hydrochloric acid to pH =

9. The resulting solid was collected by ﬁltration, washed with wa-

ter, and air-dried to give sulﬁde 8, m.p. >300^◦C, lit.²³m.p. >300^◦C

(Table IV).

(c) A solution of sulﬁde 3a (0.36 g, 1 mmol) in 5 mL of the mixture

of concentrated hydrochloric acid-ethanol (1:1) was reﬂuxed for

48 h. After cooling the resulting solid was collected by ﬁltration,

washed with ethanol, and air-dried. The product was identiﬁed

as hydrochloride of sulﬁde 10 (m.p. 208–209^◦C, Belstein test, el-

ementary analysis calcd. for C₁₉H₁₄N₂O₂S · HCl · 2H₂O (406.88)

C, 56.09; H, 4.71; N, 6.88; Cl, 8.71; S, 7.88. Found: C, 55.28; H,

4.58; N, 6.69; Cl, 9.03; S, 7.53). Neutral sulﬁde 10 was obtained

from its hydrochloride by dissolving in 2 mL of the mixture DMSO-

15% aqueous sodium hydroxide (1:3) and precipitating with 10%

hydrochloric acid to pH = 9. The resulting solid was collected by ﬁl-

tration, washed with water, and air-dried to give sulﬁde 10 (0.29 g,

87%).

1-Methyl-bis(1,4-dihydro-4-oxo-3-quinolinyl) Sulﬁde 10, m.p.

> 300^◦C

¹H NMR (DMSO-d₆) δ: 3.87 (s, 3H, NCH₃), 7.36, 7.46, 7.58 and 7.70

(4m, 4H, H-6, H-6^ꢀ, H-8 and H-8^ꢀ), 7.66 and 7.79 (2m, 2H, H-7 and H-7^ꢀ),

7.95 and 8.27 (2s, 2H, H-2 and H-2^ꢀ), 8.11 and 8.20 (2dd, 2H, H-5 and H-

5^ꢀ), 12.2 (broad, 1H, NH). EI MS (70 eV) m/z: 334 (M, 100), 317 (M-OH,

2472

K. Pluta

17.7), 302 (M-CH₃OH, 13.1). Anal. Calcd. for C₁₉H₁₄N₂OS₂(334.39); C,

68.25, H, 4.22; N, 8.38. Found: C, 68.03; H, 4.24; N, 8.19.

Alkylations of Sulﬁdes 8 and 10 with Alkylating Agents

(1) Sulﬁde 8 (0.32 g, 1 mmol) or hydrochloride of sulﬁde 8 (0.39 g, 1

mmol) was disolved in a mixture of 2 mL of DMSO, 6 mL of 15%

aqueous sodium hydroxide, and stirred with an alkylating agent

(methyl iodide, ethyl iodide, propyl iodide, allyl bromide, benzyl

chloride, methylene iodide, and 1,3-dibromopropane) at 20^◦C or

60^◦C for 24 (Table V). The resulting solid was collected by ﬁltration,

washed with water, and air-dried. The crude product was puriﬁed

by column chromatography (silica gel 60, chloroform, chloroform-

ethanol) to give sulﬁdes 9a–9e.

(2) Sulﬁde 8 (0.32 g, 1 mmol) was disolved in the mixture of 2 mL of

DMSO, 6 mL of 15% aqueous sodium hydroxide, and stirred with

methyl iodide (0.21 g, 1.5 mmol) at 20^◦C for 24 h. The resulting

solid was collected by ﬁltration, washed with water, and air-dried.

The crude product was puriﬁed by column chromatography (silica

gel 60, chloroform, chloroform-ethanol) to give sulﬁdes 9a (0.04 g,

11%). The ﬁltrate was stired with benzyl chloride (0.38 g, 3 mmol)

at 20^◦C for 24 h. The resulting solid was collected by ﬁltration,

washed with water, and air-dried. The crude product was puriﬁed

by column chromatography (silica gel 60, chloroform, chloroform-

ethanol) to give sulﬁdes 9f (0.30 g, 71%).

(3) Sulﬁde 10 (0.33 g, 1 mmol) was disolved in the mixture of 2 mL of

DMSO, 6 mL of 15% aqueous sodium hydroxide, and stirred with

benzyl chloride (0.38 g, 3 mmol) at 20^◦C for 24 h. The resulting solid

was collected by ﬁltration, washed with water, and air-dried. The

crude product was puriﬁed by column chromatography (silica gel

60, chloroform, chloroform-ethanol) to give sulﬁde 9f (0.36 g, 87%).

Bis(1-Methyl-1, 4-dihydro-4-oxo-3-quinolinyl) Sulﬁde 9a, m.p.

>310^◦C, lit.²⁸m.p. 321^◦C

¹H NMR (CDCl₃) δ: 3.85 (s, 6H, 2NCH₃), 7.38 (m, 4H, 2H-6 and 2H-8),

7.65 (m, 2H, 2H-7), 8.41 (dd, 2H, 2H-5), 8.56 (s, 2H, 2H-2).

Bis(1-Ethyl-1, 4-dihydro-4-oxo-3-quinolinyl) Sulﬁde 9b, m.p.

221–222^◦C, lit.²⁸m.p. 213^◦C

¹H NMR (CDCl₃) δ: 1.51 (t, J = 7.2 Hz, 6H, 2CH₃), 4.24 (q, J = 7.2

Hz, 4H, 2NCH₂), 7.35 (m, 2H, 2H-6), 7.41 (dd, 2H, 2H-8), 7.62 (m, 2H,

2H-7), 8.43 (dd, 2H, 2H-5), 8.61 (s, 2H, 2H-2).

Substituted 3,3^ꢀ-Diquinolinyl Sulﬁdes

2473

Bis(1-Propyl-1, 4-dihydro-4-oxo-3-quinolinyl) Sulﬁde 9c, m.p.

207–208^◦C

¹H NMR (CDCl₃) δ: 1.01 (t, J = 7.4 Hz, 6H, 2CH₃), 1.90 (q, J = 7.4

and J = 7.2 Hz, 4H, 2CH₂), 4.13 (t, J = 7.2 Hz, 4H, 2NCH₂), 7.34 (m,

2H, 2H-6), 7.38 (dd, 2H, 2H-8), 7.61 (m, 2H, 2H-7), 8.42 (dd, 2H, 2H-5),

8.58 (s, 2H, 2H-2). EI MS (70 eV) m/z: 404 (M, 100), 386 M-H₂O, 18.1),

371 (M-SH, 25.8), 361 (M-C₃H₇, 38.6). Anal. Calcd. for C₂₄H₂₄N₂O₂S

(404.52): C, 71.26; H, 5.98; N, 6.92. Found: C, 71.13; H-5.94; N, 6.73.

Bis(1-Allyl-1, 4-dihydro-4-oxo-3-quinolinyl) Sulﬁde 9d, m.p.

200–201^◦C

¹H NMR (CDCl₃) δ: 4.78 (d, J = 7.3 Hz, 4H, 2NCH₂), 5.24 (m, 4H,

2CH₂), 6.00 (m, 2H, 2CH), 7.35 (m, 2H, 2H-6), 7.36 (dd, 2H, 2H-8), 7.59

(m, 2H, 2H-7), 8.41 (dd, 2H, 2H-5), 8.56 (s, 2H, 2H-2). EI MS (70 eV)

m/z: 400 (M, 100), 385 M-CH₃, 34.9), 367 (M-SH, 18.0), 359 (M-C₃H₅,

21.5), 326 (M-C₃H₅SH, 11.3). Anal. Calcd. for C₂₄H₂₀N₂O₂S (400.49):

C, 71.98; H, 5.03; N, 6.99. Found: C, 71.73; H, 4.89; N, 6.89.

Bis(1-Benzyl-1, 4-dihydro-4-oxo-3-quinolinyl) Sulﬁde 9e, m.p.

226–227^◦C

¹H NMR (CDCl₃) δ: 5.38 (s, 4H, 2CH₂), 7.21 and 7.31 (2m, 14H, 2H-

6, 2H-8 and 2C₆H₅), 7.49 (m, 2H, 2H-7), 8.42 (dd, 2H, 2H-5), 8.72 (s,

2H, 2H-2). CI MS (70 eV) m/z: 501 (M+1, 100), 425 (M+1-C₆H₅+ H,

30.3), 411 (M+1-C₆H₅CH₂+ H, 29.9), 335 (M+1-C₆H₅CH₂C₆H₅+ 2H,

17.8). Anal. Calcd. for C₃₂H₂₄N₂O₂S (500.61): C, 76.78; H, 4.83; N, 5.60.

Found: C, 76.53; H, 4.84; N, 5.39.

1-Methyl-1^ꢀ-benzylbis(1, 4-dihydro-4-oxo-3-quinolinyl) Sulﬁde

9f, m.p. 209–210^◦C

¹H NMR (CDCl₃) δ: 3.83 (s, 3H, CH₃), 5.36 (s, 2H, CH₂), 7.20 and

7.32 (2m, 9H, C₆H₅, H-6, H-6^ꢀ, H-8 and H-8^ꢀ), 7.47 and 7.65 (2m, 2H,

H-7 and H-7^ꢀ), 8.41 and 8.42 (2dd, 2H, H-5 and H-5^ꢀ), 8.51 and 8.71

(s, 2H, H-2 and H-2^ꢀ). CI MS (70 eV) m/z: 425 (M+1, 100), 335 (M+1-

C₆H₅CH₂+ H, 30.7). Anal. Calcd. for C₂₆H₂₀N₂O₂S (424.51): C, 73.56;

H, 4.75; N, 6.60. Found: C, 73.29; H, 4.71; N, 6.41.

4,4^ꢀ-(Methylenedioxy)-3,3^ꢀ-diquinolinyl Sulﬁde 11 m.p.

240–241^◦C (dec.)

¹H NMR (CDCl₃) δ: 7.10 (s, 2H, CH₂), 7.58 (m, 2H, 2H-6), 7.74 (m,

2H, 2H-7), 8.04 (dd, 2H, 2H-8), 8.28 (dd, 2H, 2H-5), 8.91 (s, 2H, 2H-2).

¹³C NMR (CDCl₃) δ: 90.37 (CH₂), 110.18 (C-3), 122.12 (C-5), 122.37 (C-

4a), 126.96 (C-6), 129.08 (C-7), 130.73 (C-8), 149.52 (C-8a), 154.81 (C-2),

2474

K. Pluta

158.90 (C-4). EI MS (70 eV) m/z: 332 (M, 100), 302 M-CH₂O, 12.8). Anal.

Calcd. for C₁₉H₁₂N₂O₂S (332.37): C, 68.66; H, 3.64; N, 8.43. Found: C,

68.43; H, 3.54; N, 8.27.

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Article Doi

Synthesis and transformations of substituted 3,3′-diquinolinyl sulfides

DOI: 10.1080/104265090921191

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Article abstract of DOI:10.1080/104265090921191

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