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Copper-catalyzed synthesis of benzo[d][1,3]dioxin-4-ones via

tandem Ar-halogen bond hydroxylation and dichloromethane-

based double Williamson etherification

Yunyun Liu,a,* Meiying Huanga and Li Weia

aCollege of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, P. R. China

Email: chemliuyunyun@jxnu.edu.cn

General experimental information

All chemicals and solvents used in the experiments were obtained from commercial

sources and used directly without further treatment. All reactions were performed in

open air conditions. The 1H and 13C NMR were recorded in 400 MHz apparatus

usingCDCl3 as solvent, the frequency for 1H NMR and 13C NMR test are 400 MHz

and 100MHz, respectively. The chemical shifts were reported in ppm using TMS as

internalstandard. HRMS results were tested under EI or ESI model in a spectrometer

equipped with TOF analyzer. Melting points were tested in X-4A instrument without

correctingtemperature.

General procedure for the synthesis of products 3

In a 25 mL round bottom flask equipped were charged o-halobenzoic acid 1 (0.3

mmol), dichloromethane 2 (0.6 mL), KOH (2.7 mmol), Cu(OAc)2 (0.03 mmol), 8-

hydroxyquinoline (0.06 mmol), NaHCO3 (0.3 mmol) and DMF (1.5 mL). The mixture

was stirred at 110 oC for 12 h. Upon completion (TCL), the vessel was allowed to

cool down to room temperature, and 5 mL water was added. The resulting

heterogeneous mixture was extracted with ethyl acetate (3 × 10 mL). The combined

Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017

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organic phase was dried over Na2SO4. After filtering, the acquired solution was

collected and the solvent was removed at reduced pressure. The residue was then

subjected to silica gel column chromatography to give pure product by using mixed

petroleum ether and ethyl acetate (VPET : VEA = 20:1) as eluent.

Characterization data of all products

O

O

O

4H-Benzo[d][1,3]dioxin-4-one (3a).1 White solid; mp 51.2-52.4 oC; 1H NMR (400

MHz, CDCl3): δ 7.91 (dd, J1= 7.6 Hz, J2= 1.6 Hz, 1H), 7.52-7.50 (m, 1 H), 7.12 (t, J =

7.6 Hz, 1 H), 6.99 (d, J = 8.4 Hz, 1 H), 5.59 (s, 2 H); 13C NMR (100 MHz, CDCl3): δ

161.4, 158.5, 136.3, 130.4, 123.6, 116.7, 114.9, 91.1.

O

O

O

H3C

8-Methyl-4H-benzo[d][1,3]dioxin-4-one (3b).1 White solid; mp 47.2-48.1 oC; 1H

NMR (400 MHz, CDCl3): δ 7.81 (d, J = 8.0 Hz, 1 H), 7.41 (d, J = 7.2 Hz, 1 H), 7.07

(d, J = 7.6 Hz, 1 H), 5.67 (s, 2 H), 2.26 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ

161.8, 156.8, 137.2, 127.8, 126.3, 123.0, 114.6, 91.0, 14.9.

O

O

OCH3

6-Methyl-4H-benzo[d][1,3]dioxin-4-one(3c).1 Corlorless liquid; 1H NMR (400 MHz,

CDCl3): δ 7.78-7.77 (m, 1 H), 7.38 (d, J = 8.4 Hz, 1 H), 6.96 (d, J = 8.4 Hz, 1 H),

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5.63 (s, 2 H), 2.36 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ 162.6, 156.5, 137.2,

133.4, 130.1, 116.4, 114.6, 91.2, 20.6.

H3CO O

O

O

6-Methoxy-4H-benzo[d][1,3]dioxin-4-one(3d).1 White solid; mp 88.3-91.4 oC; 1H

NMR (400 MHz, CDCl3): δ 7.41 (s, J = 2.8 Hz, 1 H), 7.16 (dd, J1= 8.8 Hz, J2= 3.2

Hz, 1 H), 7.00 (d, J = 8.8 Hz, 1 H), 5.63 (s, 2 H), 3.83 (s, 3H); 13C NMR (100 MHz,

CDCl3): δ 161.6, 155.5, 152.8, 124.9, 117.9, 115.0, 111.3, 91.3, 55.9.

O

O

O

F

7-Fluoro-4H-benzo[d][1,3]dioxin-4-one (3e).1 White solid; 55.2-56.1 oC; 1H NMR

(400 MHz, CDCl3): δ 8.03 (dd, J1 = 8.8 Hz, J2 = 2.8 Hz, 1 H), 6.93-6.88 (m, 1 H),

6.78 (dd, J1 = 8.8 Hz, J2 = 2.4 Hz, 1 H), 5.67 (s, 2 H); 13C NMR (100 MHz, CDCl3):

δ168.61, 166.05, 160.50, 160.02 (d, J = 13.0 Hz), 133.01 (d, J = 11.3 Hz), 112.09 (d,

J = 22.9 Hz), 11.38 (d, J = 2.7 Hz), 104.35 (d, J = 24.3 Hz), 91.36.

FO

O

O

6-Fluoro-4H-benzo[d][1,3]dioxin-4-one(3f).1 White solid; mp 96.5-97.4 oC; 1H

NMR (400 MHz, CDCl3): δ 7.dd (dd, J1 = 8.4 Hz, J2 = 4.8 Hz, 1 H), 7.34-7.27 (m, 1

H), 7.08 (dd, J1 = 8.8 Hz, J2= 4.8 Hz, 1 H), 5.66 (s, 2 H); 13C NMR (100 MHz,

CDCl3): δ 160.50 (d, J = 2.3 Hz), 159.36, 156.93, 154.69 (d, J= 2.7 Hz), 123.81 (d, J

= 23.7 Hz), 118.44 (d, J = 8.5 Hz), 115.75 (d, J = 24.2 Hz), 91.4.

O

O

OF

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5-Fluoro-4H-benzo[d][1,3]dioxin-4-one (3g). White solid; mp 79.1-80.5 oC; 1H

NMR (400 MHz, CDCl3): δ 7.50-7.44 (m, 1 H), 6.84 (t, J = 8.0 Hz, 2 H), 5.57 (s, 2

H); 13C NMR (100 MHz, CDCl3): δ 164.16, 161.51, 159.49 (d, J = 2.2 Hz), 157.28,

136.67 (d, J = 10.7 Hz), 112.49 (d, J = 4.1 Hz), 111.22 (d, J = 20.8 Hz), 90.97; EI-

HRMSCalcd for C8H5FO3 [M]+168.0223, found168.0229.

O

O

O

Cl

7-Chloro-4H-benzo[d][1,3]dioxin-4-one(3h).1 White solid; mp 98.7-99.5 oC; 1H

NMR (400 MHz, CDCl3): δ 7.94 (d, J = 8.0 Hz, 1 H), 7.20-7.17 (m, 1 H), 7.11 (s, 1

H), 5.68 (s, 2 H); 13C NMR (100 MHz, CDCl3): δ 160.6, 158.8, 142.4, 131.6, 124.5,

117.2, 113.4, 91.3.

O

O

OCl

6-Chloro-4H-benzo[d][1,3]dioxin-4-one (3i).1 White solid; mp 102.3-103.3 oC; 1H

NMR (400 MHz, CDCl3): δ 7.97 (d, J = 8.4 Hz, 1 H), 7.54 (dd, J1 = 8.8 Hz, J2 = 2.8

Hz, 1 H), 7.05 (d, J = 8.8 Hz, 1 H), 5.67 (s, 2 H); 13C NMR (100 MHz, CDCl3): δ

160.3, 156.9, 136.4, 129.8, 129.1, 118.4, 116.0, 91.2.

O

O

O

Cl

5-Chloro-4H-benzo[d][1,3]dioxin-4-one (3j). White solid; mp 106.8-108.3 oC; 1H

NMR (400 MHz, CDCl3): δ 7.46 (t, J = 8.0 Hz, 1 H), 7.25 (t, J = 8.0 Hz, 1 H), 7.01

(d, J = 8.0 Hz, 1 H), 5.64 (s, 2 H); 13C NMR (100 MHz, CDCl3): δ 160.2, 158.0,

137.1, 135.4, 126.6, 115.6, 113.2, 90.6; EI-HRMS Calcd for C8H5O3Cl

[M]+183.9927, found 183.9936.

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IO

O

O

6-Iodo-4H-benzo[d][1,3]dioxin-4-one (3k). White solid; mp 112.6-114.3oC; 1H

NMR (400 MHz, CDCl3): δ 8.29 (d, J = 2.0 Hz, 1 H), 7.85 (dd, J1 = 8.8 Hz, J2 =

2.0Hz, 1 H), 6.86 (d, J = 8.4 Hz, 1 H), 5.66 (s, 2 H); 13C NMR (100 MHz, CDCl3): δ

159.9, 158.0, 144.8, 138.8, 119.0, 116.8, 91.2, 85.8; ESI-HRMS Calcd for C8H6IO3

[M + H]+ 276.9356, found 276.9357.

O

O

OF

F

6,7-Difluoro-4H-benzo[d][1,3]dioxin-4-one (3l). White solid; mp 92.5-94.1 oC; 1H

NMR (400 MHz, CDCl3): δ 7.82 (t, J = 8.8 Hz, 1 H), 6.94 (dd, J1 = 10.0 Hz, J2 = 4.0

Hz, 1 H), 5.69 (s, 2 H); 13C NMR (100 MHz, CDCl3): δ 159.74, 156.65 (d, J = 17.4

Hz), 155.38 (d, J = 10.7 Hz), 148.19 (d, J = 14.0 Hz), 145.75 (d, J = 11.5 Hz), 118.10

(dd, J1 = 3.5 Hz, J2 = 19. 6 Hz), 106.23 (d, J = 21.5 Hz), 91.55; EI-HRMS Calcd for

C8H4F2O3 [M]+ 186.0123, found 186.0135.

O

O

O

I

I

6,8-Diiodo-4H-benzo[d][1,3]dioxin-4-one (3m). White solid; mp 126.7-128.3 oC; 1H

NMR (400 MHz, CDCl3): δ 8.29 (s, 2H), 8.27 (s, 1 H), 5.73 (s, 2 H); 13C NMR (100

MHz, CDCl3): δ 160.6, 158.8, 142.4, 131.6, 124.4, 117.2, 113.4, 91.3.

Reference

1 Lin, F.; Song, Q.; Gao, Y.; Cui, X. RSC Adv. 2014, 4, 19856.

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1H and 13C NMR spctra of 3a

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1H and 13C NMR spctra of 3b

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1H and 13C NMR spctra of 3c

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1H and 13C NMR spctra of 3d

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1H and 13C NMR spctra of 3e

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1H and 13C NMR spctra of 3f

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1H and 13C NMR spctra of 3g

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1H and 13C NMR spctra of 3h

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1H and 13C NMR spctra of 3i

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1H and 13C NMR spctra of 3j

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1H and 13C NMR spctra of 3k

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1H and 13C NMR spctra of 3l

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1H and 13C NMR spctra of 3m