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Tong-Shou Jin*, Li-Bin Liu, Ying Yin, Ying Zhao and Tong-Shuang Li. College of Chemistry and Environmental Science, Hebei University, Baoding 071002, ...

Letters in Organic Chemistry, 2006, 3, 591-596

591

Clean Synthesis of 14-Alkyl and 14-Aryl-14-H-dibenzo[a,j]xanthenes Tong-Shou Jin* , Li-Bin Liu, Ying Yin, Ying Zhao and Tong-Shuang Li College of Chemistry and Environmental Science, Hebei University, Baoding 071002, P. R. China Received June 10, 2006: Revised July 29, 2006: Accepted August 04, 2006

Abstract: Two clean and efficient methods for the synthesis of 14-alkyl and 14-aryl-14-H-dibenzo[a,j] xanthenes are described: (1) in aqueous media, using p-dodecylbenezenesulfonic acid (DBSA) as the catalyst (20 mol%), under heat conditions. (2) Under solvent-free condition, using p-toluene sulfonic acid (p-TSA) as catalyst and in microwave irradiation.

Keywords: 14-Alkyl and 14-aryl-14-H-dibenzo[a,j]xanthenes, -naphthol, aldehyde, aqueous media, microwave irradiation, clean synthesis. INTRODUCTION The preparation of xanthenes, especially benzoxanthenes, have attracted strong interest due to the broad spectrum of their biological and pharmaceutical properties such as antibacterial [1], antiviral [2] and anti-inflammatory [3] activities as well as efficacy in photodynamic therapy [4] and antagonists for the paralyzing action of zoxazolamine [5]. Furthermore, these compounds can be employed as laser technologies [6], pH-sensitive fluorescent materials for visualization of biomolecules [7] and dyes [8]. The reported syntheses of xanthenes and benzoxanthenes were significant in number such as the cycloacylation of carbamates [9], trapping of benzynes by phenols [10], cyclocondensation

synthesis of benzoxanthenes has been achieved by the reaction of aldehydes with -naphthol by dehydration [13]. Other routes for the synthesis of benzoxanthenes have also been reported including the reaction of β-naphthol with formamide [14], carbon monoxide [15], aldehyde acetals [13a] and 2-naphthol-1-methanol [16], but each of the above methods has its own merit. However, some of these methods have not been entirely satisfactory owing to such drawbacks as low yield, long reaction times (16 h to 5 d), use of toxic organic solvent, special apparatus and harsh reaction conditions. More recently, some methods were reported again for the synthesis of this kind of compound to obtain relatively better results [17,18].

R OH RCHO +

2

H2O, reflux, DBSA or solvent-free, M WI, p-TSA

1

3

2

O

Scheme 1. O

OH OHCCHO +

1n

4

H2O, reflux, DBSA

2

O 4

Scheme 2.

reaction between 2-hydroxyaromatic aldehydes and 2tetralone [11] and intramolecular phenylcarbonyl coupling reaction of benzaldehydes and acetophenones [12]. The *Address correspondence to this author at the College of Chemistry and Environmental Science, Hebei University, No.88 Hezuo Road, Baoding 071002, Hebei Province, P. R. China; Fax: +86 (312) 5079628; E-mail: [email protected] 1570-1786/06 $50.00+.00

Recently, organic reactions in water have attracted much attention, because water is a cheap, safe and environmentally benign solvent [19]. DBSA has been used in a number of organic reactions as a good catalyst. In the course of our investigations to develop new synthetic methods in water using DBSA as catalyst, we examined the synthesis of 14-alkyl and 14-aryl- 14-H-dibenzo[a,j]xanthenes (Scheme 1) and 14,14’-bis-(14-H-dibenzo[a,j]xanthenes) (Scheme 2) in © 2006 Bentham Science Publishers Ltd.

592

Letters in Organic Chemistry, 2006, Vol. 3, No. 8

Table 1.

Jin et al.

Synthesis of 14-Alkyl and 14-Aryl-14-H-Dibenzo[a,j]xanthenes and 14,14’-Bis(14-H-dibenzo[ a,j]- xanthenes) Aldehyde

Entry

Method A a

Product

Method Ba

Mp ( o C)

Time (h)

Yieldb (%)

Time (min)

Yield b (%)

Found

Reported

18

33

10

81

181-182

185 [13d]

20

93

13

93

312-313

310 [13d]

18

84

8

90

212-213

211 [13e]

16

43

10

92

301-302

—c

—c

8

87

202-203

CHO 1

O

1a

O2N 2

CHO

1b

O

NO2

O2N CHO 3 1c

O NO2

Cl 4

CHO 1d

O

Cl

Cl CHO 5 1e

O Cl

Clean Synthesis of 14-Alkyl and 14-Aryl-14-H-dibenzo[a,j]xanthenes

Letters in Organic Chemistry, 2006, Vol. 3, No. 8

593

(Table 1). contd.....

Entry

Aldehyde

Method A a

Product

Method Ba

Mp ( o C)

Time (h)

Yieldb (%)

Time (min)

Yield b (%)

Found

Reported

18

72

10

88

216-218

215 [13e]

16

44

10

94

300-302

297 [13d]

—c

—c

8

95

194-195

192 [13e]

—c

—c

10

69

206-208

204 [13e]

—c

—c

12

77

240-241

18

77

8

86

331-333

Cl CHO Cl

6

1f

Br

O

CHO

7

1g

O

Br

CHO 8

Br 1h

O Br

H3CO 9

CHO

1i

O 10

O

OCH3

CHO O 1j O

O O

OHC 11

CHO

1k

O

CHO

594

Letters in Organic Chemistry, 2006, Vol. 3, No. 8

Jin et al.

(Table 1). contd.....

Entry

12

Aldehyde

CH3 CHO O

1l

13

OHCCHO

Method Ba

Mp ( o C)

Time (h)

Yieldb (%)

Time (min)

Yield b (%)

Found

Reported

20

82

8

31

169-170

173 [13a]

—c

—c

8

42

204-206

24

76

—c

—c

235-236

CH3

HCHO O

1m

14

Method A a

Product

O

O

1n

a Method A: heat reflux in aqueous media; Method B: solvent-free under microwave irradiation. bIsolated yields. c no reaction

water, as a green solvent. Dry methods using microwave heating have attracted much more attention [20-22], because avoiding organic solvents during the reactions leads to clean, efficient and economical technology. We herein describe the synthesis of 14-alkyl and 14-aryl-14-H-dibenzo[a,j]xanthenes (Scheme 1) by the reaction of various aldehydes with -naphthol in water, as a green solvent, using DBSA as catalyst (Method A), as well as under microwave irradiation using free solvent conditions and p-TSA as catalyst (Method B). The first procedure was also applied to the synthesis of 14,14’-bis-(14-H-dibenzo[a,j]xanthenes) (Scheme 2). The results are summarized in Table 1. In the method A, the catalyst (DBSA) played a crucial role in the success of the reaction in terms of the rate and the yields. For example, 4-chlorobenzaldehyde reacted with 2naphthol in the presence of 5 mol% DBSA to give the product 3d in poor yield (11.2%) at refluxing water after sixteen hours of reaction time. Increasing of the catalyst to 10 and 20 mol% resulted in the reaction yields to 36.9% and 43.1%, respectively. Higher amounts of the catalyst did not improve the results to a greater extent. The reaction could not be carried out in the absence of DBSA. Thus, 20 mol% DBSA was chosen as an appropriate quantit for these reactions.

In method B, according to the results we have obtained in Table 1, the nature of substituting group on the aromatic ring showed some effect on this conversion. Benzaldehyde and other aromatic aldehydes carrying electron-withdrawing groups (entries 1a-1h and 1k) reacted well under microwave irradiation with high yields. However, aromatic aldehydes with electron-donating groups (entries 1i and 1j) can only give the products in moderate yields. The explanation for this result may be due to the electron-donating group in 1i and 1j, which will reduce reactivity of the corresponding aldehyde group, making it less electrophilic. In addition, the reaction of aromatic aldehyde or aliphatic aldehyde and βnaphthol gave different experimental results. From Table 1, we know that aromatic aldehyde gives better results than aliphatic aldehyde. For instance, acetaldehyde 1l and formaldehyde 1m reacted with β-naphthol under microwave irradiation and gave yields of 3l (31%) and 3m (42%), respectively. In conclusion, we have described two clean and efficient methods for the synthesis of 14-alkyl and 14-aryl-14-Hdibenzo[a,j]xanthenes: (1) in aqueous media, using pdodecylbenzenefonic acid (DBSA) as the catalyst (20 mol%), under heat conditions; (2) in solvent-free condition, in the presence of p-toluene sulfonic acid (p-TSA) as catalyst, under microwave irradiation. In addition, it is possible to

Clean Synthesis of 14-Alkyl and 14-Aryl-14-H-dibenzo[a,j]xanthenes

apply the tenets of green chemistry to the generation of biologically interesting products using aqueous media and solvent free approaches, which are less expensive and less toxic than those with organic solvents. Moreover, the procedure offers several advantages including high yields, operational simplicity, cleaner reactions and minimal environmental impact, which makes it a useful and attractive process for the synthesis of these compounds. EXPERIMENTAL SECTION The new compounds prepared were characterized by 1H NMR, IR and element analysis and are described in the experimental section. IR spectra were recorded on a Bio-rad FIS-40 spectrometer (KBr). 1H NMR spectra were measured at 400 MHz on an AVAVCE-400 spectrometer using TMS as internal standard and DMSO as solvent. Elemental analyses were determined using Perkin-Elmer 2400 II elemental analyzer.

Letters in Organic Chemistry, 2006, Vol. 3, No. 8

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(d, J=8.4 Hz, 2H) ppm. Anal. calcd. for C27H17ClO: C, 82.54; H, 4.36. Found: C, 82.40; H, 4.52. 14-(3, 4-Dioxymethylenephenyl)-14-H-dibenzo[a,j]xanthene (3j) IR (KBr): νmax= 3065, 2886, 1622, 1591, 1457, 1434, 1398, 1245, 1037, 960, 926, 818, 804cm-1 . 1H NMR (400 MHz, DMSO): δ = 5.77 (s, 2H), 6.46 (s, 1H), 6.62 (d, J=8.0 Hz, 1H), 6.91 (s, 1H), 7.12 (d, J=8.0 Hz, 1H), 7.437.51 (m, 4H), 7.60 (t, J=8.0 Hz, 2H), 7.81 (dd, J1=18.0Hz, J2=8.0 Hz, 4H), 8.39 (d, J=8.4 Hz, 2H) ppm. Anal. calcd. for C28H18O3: C, 83.57; H, 4.51. Found: C, 83.75; H, 4.40. 14-(4-Formacyl)-14-H-dibenzo[a,j]xanthene (3k)

General Procedure for the Preparation of the Products 3 and 4

IR (KBr): νmax= 3057, 2829, 2741, 1691, 1601, 1573, 1515, 1458, 1432, 1401, 1240, 1030, 962, 821cm-1 . 1H NMR (400 MHz, DMSO): δ = 6.87 (s, 1H), 7.46 (m, 2H), 7.59 (d, J=8.8 Hz, 2H), 7.63 (t, J=7.6Hz, 2H), 7.70 (d, J=7.6 Hz, 2H), 7.87 (d, J=8.0 Hz, 2H), 7.95 (t, J=8.0 Hz, 4H), 8.69 (d, J=8.4 Hz, 2H), 9.78 (s, 1H) ppm. Anal. calcd. for C28H18O2: C, 87.03; H, 4.69, Found: C, 87.11; H, 4.51.

Method A

14,14-H-Dibenzo[a,j]xanthene (3m)

A mixture of aldehyde (1) or (1n), β-naphthol (2) and DBSA (20 mol%) in water (20 mL) was stirred at refluxing for several hours. The progress of the reaction was monitored by TLC. After completion of the reactions, the mixture was cooled to room temperature and the solid was filtered, washed with H2O (40 mL), ethanol (95%) (20mL) and the resulting crude product was purified by recrystallization from DMF-ethanol.

IR (KBr): νmax= 3048, 2834, 1639, 1619, 1513, 1459, 1433, 1402, 1241, 1026, 960, 905, 804 cm-1 . 1H NMR (400 MHz, DMSO): δ = 4.69 (s, 2H), 7.37 (d, J=8.8 Hz, 2H), 7.51 (t, J=7.6 Hz, 2H), 7.67 (t, J=7.6 Hz, 2H), 7.81 (d, J=8.8 Hz, 2H), 7.90 (d, J=8.0 Hz, 2H),8.09 (d, J=8.4 Hz, 2H) ppm. Anal. calcd. for C21H14O: C, 89.34; H, 5.00. Found: C, 89.19; H, 5.09.

Method B

IR (KBr): νmax= 3053, 3023, 1914, 1630, 1619, 1596, 1521, 1466, 1255, 1058, 964, 905, 810 cm-1 . 1H NMR (400 MHz, DMSO): δ = 5.61 (d, J=6.0 Hz, 2H), 7.24 (m, 4H), 7.34 (t, J=7.6 Hz, 4H), 7.53 (t, J=7.2 Hz, 4H), 7.76 (d, J=8.8 Hz, 4H), 7.82 (d, J=8.4 Hz, 4H), 8.30 (d, J=8.4 Hz, 4H) ppm. Anal. calcd. for C42H26O2: C, 89.66; H, 4.66. Found: C, 89.78; H, 4.55.

A mixture of aldehyde (1), β-naphthol (2), and p-TSA (10 mol%) was well ground with a pestle and introduced to microwave irradiation at 425 watts in an open Pyrex beaker for the length of time indicated in Table 1. The reaction was monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature ethanol (10 mL) was added. The mixture was poured into 80 mL ice-water, the solid was filtered, washed with H2O (40 mL), ethanol (95%) (20mL) and the resulting crude product was purified by recrystallization from DMF-ethanol. Data of Some New Compounds are Shown Below 14-(4-Chlorophenyl)-14-H-dibenzo[a,j]xanthene (3d) IR (KBr): νmax= 3063, 2924, 1623, 1591, 1578, 1457, 1435, 1398, 1240, 1075, 961, 812 cm-1 . 1H NMR (400 MHz, DMSO): δ = 6.50 (s, 1H), 7.12 (d, J=8.0 Hz, 2H), 7.45-7.52 (m, 6H), 7.61 (t, J=7.6 Hz, 2H), 7.82 (dd, J1=14.0 Hz, J2=8.4 Hz, 4H), 8.34 (d, J=8.4 Hz, 2H) ppm. Anal. calcd. for C 27H17ClO: C, 82.54; H, 4.36. Found: C, 82.65; H, 4.40.

14,14’-Bis(14-H-dibenzo[a,j]xanthenes) (4)

ACKNOWLEDGEMENTS This project was supported by the National Natural Science Foundation of China (29872011), Educational Ministry of China, Educational Department of Hebei Province, Science and Technology Commission of Hebei Province. REFERENCES [1] [2] [3] [4]

14-(3-Chlorophenyl)-14-H-dibenzo[a,j]xanthene (3e) IR (KBr): νmax= 3065, 2921, 1625, 1590, 1572, 1458, 1430, 1398, 1243, 1080, 961, 837, 812 cm-1 . 1H NMR (400 MHz, DMSO): δ = 6.50 (s, 1H), 7.00 (d, J=8.0 Hz, 1H), 7.09(t, J=8.0 Hz, 1H), 7.44-7.53 (m, 6H), 7.61 (t, J=8.0 Hz, 2H), 7.82 (dd, J1=13.6 Hz, J2=8.4 Hz, 4H), 8.34

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