the Dual Role of Acyl Halides - ACS Publications

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Copper-Catalyzed One-Pot N-Acylation and C5-H Halogenation of 8-Aminoquinolines: the Dual Role of Acyl Halides Yi Du, Yunyun Liu, and Jie-Ping Wan J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00068 • Publication Date (Web): 02 Mar 2018 Downloaded from http://pubs.acs.org on March 2, 2018

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The Journal of Organic Chemistry

Copper-Catalyzed One-Pot N-Acylation and C5-H Halogenation of 8-Aminoquinolines: the Dual Role of Acyl Halides Yi Du,a Yunyun Liu,* Jie-Ping Wan* College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, China E-mail: [email protected]; [email protected]

Abstract The synthesis of N-acyl-5-halo-8-aminoquinolines has been realized by directly employing 8-aminoquinolines and acyl halides (Cl, Br, I) with copper catalysis. The construction of the target products involves in domino N-acylation and C5-H halogenations of the 8-aminoquinoline wherein the acyl halides act as the donors of both acyl and halide atom, which enables the first access to the step efficient synthesis of 5-halogenated N-acyl quinlolines. Quinoline is a heterocyclic moiety of strategic importance because of the ubiquitous utilities of quinoline derivatives in pharmaceutical chemistry, drug discovery, clinic medicine, fine organic synthesis and meterials science etc.1 Therefore, exploring the synthetic approaches of quinolines with diverse substructures 1

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represents crucial task.2 Generally, the major known methodologies toward the synthesis of quinolines can be divided into two different prototypes: the synthesis involving the quinoline ring construction and the direct elaboration on simple quinoline ring. While both tactics contributed indispensably to the development of quinoline chemistry, the latter one has in recent years attracted extensive attention due to the occurrence of those efficient quinoline C-H bond activation reactions. Most notably, the direct C5-H functionalization of quinolines has witnessed spectacular progress, and the functionalization of this C-H bond forging both new C-C3 and C-heteroatom4 bonds has won great success. Among the research works on quinoline C5-H functionalization, extraordinary efforts have been made in the C-H halogenation reaction with the assistance of an amide directing group. Ertem and Stahl firstly observed and analyzed the single electron transfer (SET)-based C-5 chlorination of 8-amidoquinoline.5 Later on, a number of catalytic methods employing various halogen sources have been successively reported, including the halogenation using NXS (X = Cl, Br or I) with transition metal-catalysis,6 the transition metal-free oxidative C-H halogenation using NXS,7 transition metal-catalyzed reactions using halide salts,8 transition metal-free oxidative C-H halogenation using halide salts,9 and the C-H iodination using molecular idodine.10 Despite these noticeable advances, two major challenges remain to overcome. The first one is that the 8-amido quinolines substrates need to be prior prepared by the N-acylation of commercial 8-aminoquinoline; the second one is that additional halogen source (NXS, metal halides, iodine and other halogen reagents) are 2


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mandatory for all the known methods of such halogenation (A, Scheme 1). The additional chemical consumption resulting from the intermediate purification, different halogen sources as well as the chemical wastes resulting from these operations are against the criteria of sustainable synthesis. Considering the significance of establishing more efficient arene C-H halogenation reactions,11 developing alternative methods which can overcome one or more of the limits is highly desirable for 5-halo-8-amidoquinolien synthesis. Acyl halides (mainly chlorides) are simple and widespread utilized reagents, their application mainly focuses on the utility as acylating reagents toward both C-H12, heteroatom-H,13 and C-heteroatom bonds.14 In addition, some protocols involving cascade bond transformations on the acyl chloride are also known.15 In all these reactions, the chlorine atom in the acyl chloride is released after reaction as either hydrochloric acid or chloride salt without showing application in the construction of the products. Therefore, probing new synthetic application of the acyl halides as the donor of halogen source is quite interesting. Herein, we report the first example on the one-step synthesis of 5-halogenated N-acyl 8-aminoquinolines via the reactions of 8-aminoquinolines and acyl halides through tandem N-acylation and C-H halogenation wherein the acyl halides act as both the acylating and halogenating reagents (B, Scheme 1). Scheme 1 Stepwise vs one-step synthesis of 5-halogenated 8-aminoquinolines

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A) Known: conventional procedure for 5-halogenated-8-amidoquinolines synthesis X RCOCl

purification "X" source

N-acylation

N

step 1

NH2

N HN

N

step 2

HN

COR

COR

B) This work: one-step synthesis of 5-halogenated-8-amidoquinolines synthesis with the dual role of acyl chlorides X R1

R2COX N NH2

one-step N-acylation and C-H halogenation no additional "X" source one-step

X = Cl, Br, I

R1 N HN

COR

To start the work, the reaction of 8-aminoquinoline 1a and n-butyryl chloride 2a was tentatively run in the presence of CuO. Fortunately, this entry in toluene gave the 5-chlorinated aminoquinoline 3a with good yield (entry 1, Table 1). When Cu(OAc)2 was employed, lower yield of 3a was found (entry 2, Table 1). In addition, using CuBr2 as catalyst resulted in the formation of mixed chlorinated and brominated products (see Eq 6 in the control experiment). Notably, utilizing base additive of different potency all led to the inhibition of the target transformation and only the amide intermediate from amidation of 2a was observed (entries 3-6, Table 1), probably because of the negative effect of a base to the generation of reactive CuX2 by neutralizing the in situ produced acid HX (see also the mechanism in Scheme 2). Furthermore, in the reactions conducted in different media, xylene was identified as the most appropriate candidate (entries 7-11, Table 1). While no enhanced yield of 3a was observed in the entries with different catalyst loadings (entries 12-13, Table 1), the reaction run at higher temperature led to slight increase of the product yield (entries 14-16, Table 1). Successively, the effects of acid additive and acyl chloride loading to the reaction were investigated, and no improvement was observed (entries 17-19, Table 1). An entry conducted under nitrogen provided 3a with 32% yield, suggesting that air was important for the reaction (entry 20, Table 1). Finally, a control 4


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entry employing CuCl2 as catalyst was conducted under other optimized parameters, but no superior yield of the chlorinated product 3a was observed, implying against the positive effect the halogen anion in the copper(II) salt to the reaction (entry 21, Table 1). Moreover, no formation of Cl2 was observed on the optimized model reaction with the examination by AgNO3 solution. Table 1. Optimization of reaction conditionsa

Entry

Catalyst

Additive

Solvent

T (oC)

Yield(%)b

1

CuO

-

toluene

110

72

2

Cu(OAc)2

-

toluene

110

20

3

CuO

K2CO3

toluene

110

NR

4

CuO

KOH

toluene

110

NR

5

CuO

Cs2CO3

toluene

110

NR

6

CuO

Na2CO3

toluene

110

NR

7

CuO

-

DMF

110

60

8

CuO

-

xylene

110

74

9

CuO

-

1,4-dioxane

110

NR

10

CuO

-

DMSO

110

NR

11

CuO

-

DCE

110

NR

12c

CuO

-

xylene

110

73

13d

CuO

-

xylene

110

66

14

CuO

-

xylene

120

77

15

CuO

-

xylene

80

64

16

CuO

-

xylene

60

40 5



a

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17

CuO

TFA

xylene

120

23

18e

CuO

-

xylene

120

22

19f

CuO

-

xylene

120

66

20g

CuO

-

xylene

120

32

21 CuCl2 xylene 120 68 Gerenal conditional: 1a (0.2 mmol), 2a (0.4 mmol), catalyst (0.08 mmol), additive

(0.4 mmol), solvent (2 mL), stirred for 6h; NR = no reaction. bIsolated yield based on 1a. cCuO (0.12 mmol). dCuO (0.04 mmol). eWith 0.2 mmol acyl chloride 2a. fWith 0.6 mmol acyl chloride 2a. gUnder nitrogen. In the section of scope investigation, different acyl chlorides were firstly subjected for the synthesis. Notably, both linear and branched alkyl functionalized acyl chlorides exhibited fine tolerance to the synthesis of corresponding products with good to excellent yield (3a-3f, Table 2). In addition, benzoyl chlorides containing various substituents in the phenyl ring also smoothly took part in the titled synthesis (3g-3n, Table 2). Moreover, the successful synthesis of products 3o-3q and 3r using phenylacetyl chlorides and heteroaroyl chloride as starting materials further confirmed the general applicability of the acyl chloride component in this synthetic approach. Delightfully, synthesis of 5-brominated quinoline product 3t could also be easily accessed by simply utilizing acyl bromide. The yield of the product was lower possibly becausethat acyl bromide was more sensitive to moisture. Actually, the expected synthesis of corresponding brominated product was not successful under the present reaction condition when acetyl bromide or α-bromoacetyl bromide was used, respectively. As for the synthesis of 5-iodo-8-amidoquinoline, because of the low stability of the acyl iodide, a one-pot procedure allowing in situ generation of acyl 6


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Table 2 Scope of the copper-catalyzed tandem N-acylation and C5-H halogenationsa,b

a

General conditions: 1 (0.2 mmol), 2 (0.4 mmol), CuO (0.08 mmol) in xylene (2 mL),

stirred at 120 oC for 6 h. bIsolated yield based on 1.

iodide and subsequent reaction without isolating the acyl iodide was designed and conducted. Firstly, the acyl iodide was prepared following literature process,16 and the acyl iodide generated therein was directly subjected to the standard condition with 1a. As expected, 5-iodinated product 3u was readily acquired with fair yield (Eq 1). On the basis of these entries, the reactions employing non-aromatic amines instead of 8-aminoquinoline was also attempted. However, only the amides resulting from the amidation of acyl chloride were observed when aniline and 1-aminonaphthalene was employed, respectively.

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To gain information on the possible process of the C-H chlorination, some control experiments were then executed. Firstly, the direct employment of N-benzoyl 8-aminoquinoline 4 and benzoyl chloride gave target product 3g with good yield under the standard conditions (Eq 2). This result as well as the known literatures on similar N-amidoquinoline C-5 halogenation supported that 4 was the key intermediate in the reaction. On the other hand, the reaction of 4 with stoichiometric NaCl didn’t provide the chlorinated product (Eq 3), identical consequence occurred even when Me4NCl (1 equiv) and water (0.5 mL) were additionally employed. However, using 1 equiv 37% concentrated hydrochloric acid as the source of chlorine gave 3g with fair yield (Eq 4), suggesting that the acidic conditions was important in enabling the C-H halogenation. Much lower product yield was afforded by the same reaction in the presence of 1 equiv phase transfer reagent Me4Cl. Utilizing CuCl2 as the chlorine source to reaction with amide 4 did provide product 3g with fair yield, implying that the halogen anion in the copper(II) salt could also act as the source of halogen in the target product (Eq 5). Actually, performing the model reaction using CuBr2 as catalyst resulting in the production of mixed chlorinated and brominated products, further confirmed this conclusion (Eq 6). On the other hand, employing CuCl2 as catalyst for the reaction of propionyl bromide gave main the brominated product, albeit in low yield (Eq 7). The result form this reaction indicated that the halogen anion in the acyl halide was much more active halogen source, and the low yield might be ascribed to the inferior catalytic activity of CuCl2 by getting transformed in the less reactive CuBr2. A reaction employing directly 8-aminoquinoline 1a and CuCl2 in the presence 8


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of CuO didn’t give chlorinated product 5a (Eq 8), implying that that the aryl C-H halogenation might not be the first transformation step.

Following the information provided by the control experiments, a plausible mechanism for the reactions providing N-acyl 5-halo-8-aminoquinolines is proposed and outlined in Scheme 2. At the beginning, the N-acyl 8-aminoquinoline 4 is generated via the reaction of 8-aminoquinoline 1 and acycl halide 2, the simultaneously generated acid may convert the CuO catalyst into CuX2 which can easily couple 4 to give Cu(II) complex A.8c, f The intramolecular SET on A then provides Cu(I) species B containing reactive halogen anion via analogous process in literature.11a The migration of the X- to the C-5 position gives rise to Cu(I) radical C, and the decomposition of

C may produce the product 3, Cu(I) and hydrogen radical.

The aerobic oxidation on the resulting Cu(I) regenerates Cu(II) which can both take part in the repeated catalytic cycle and get reduced to Cu(I) by incorporating the hydrogen radical. Scheme 2 The proposed reaction mechanism

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In conclusion, we have developed for the first time a step efficient route to the synthesis of N-acylated 5-halo-8-aminoquinolines via the direct reactions of 8-aminoquinolines and acyl halides. The synthetic reactions proceeds well via the catalysis of CuO without using additional halogen source, and show general tolerance to acyl halide (Cl, Br and I). In addition, not any ligand, oxidant, acid or base additive is required. Owing to these unique advantages, the present method can thus be a useful complement to the known synthesis of 5-halogenated quinoline scaffolds.

Experimental Section

General information

Reagents and organic solvents used in the experiments are purchased from commercial source, and used without further treatment. Solvents have been treated following standard procedure. All the reactions were performed under air atmosphere. The 1H and 13C NMR were recorded in 400 MHz apparatus using CDCl3 as solvent, The chemical shifts were reported in ppm with reference to the TMS internal standard. 10


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HRMS results were tested under ESI model in a spectrometer equipped with TOF analyzer. The melting points are measured in X-4A apparatus without correcting the temperature.

General procedure for the synthesis of products 3a-3s

In a 25 mL round bottom flask equipped with a condenser were charged 8-aminoquinoline 1 (0.2 mmol), acyl chloride/bromide 2a (0.4 mmol), CuO (0.08 mmol) and xylene (2 mL), the mixture was heated at 120 oC for 6 h with stirring under air atmosphere. Upon completion (TLC), the vessel was allowed to cool down to room temperature, and 10 mL water was added. The resulting suspension was extracted with ethyl acetate (3 × 10 mL), and the combined organic phase was dried over Na2SO4. The solution was then obtained via simple filtration, and solution was provided therein was subjected to reduced pressure to remove the solvent. The residue was then employed to silica gel column chromatography, and the pure product was acquired by using petroleum ether / ethyl acetate (VPET: VEA = 35:1) as eluent. N-(5-Chloroquinolin-8-yl)butyramide (3a).17 Yield 77%, 38 mg; white solid; mp 64-65 oC; Rf = 0.29; 1H NMR (400 MHz, CDCl3): δ 9.73 (s, 1 H), 8.81 (dd, J = 4.3, 1.6 Hz, 1 H), 8.71 (d, J = 8.4 Hz, 1 H), 8.52 (dd, J = 8.5, 1.6 Hz, 1 H), 7.60-7.47 (m, 2 H), 2.54 (t, J = 7.5 Hz, 2 H), 1.90-1.82 (m, J = 7.4 Hz, 2 H), 1.06 (t, J = 7.4 Hz, 3 H); 13

C NMR (100 MHz, CDCl3): δ 171.9, 148.7, 139.0, 133.9, 133.6, 127.4, 126.0, 124.2,

122.4, 116.5, 40.3, 19.2, 13.9.

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N-(5-Chloroquinolin-8-yl)propionamide (3b).17 Yield 92%, 43 mg; white solid; mp 82-83 oC; Rf = 0.26; 1H NMR (400 MHz, CDCl3): δ 9.79 (s, 1 H), 8.85 (dd, J = 4.3, 1.6 Hz, 1 H), 8.74 (d, J = 8.4 Hz, 1 H), 8.58 (dd, J = 8.5, 1.6 Hz, 1 H), 7.67-7.51 (m, 2 H), 2.60 (q, J = 7.5 Hz, 2 H), 1.34 (t, J = 7.5 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 172.5, 148.6, 138.9, 133.9, 133.4, 127.3, 125.9, 124.1, 122.4, 116.4, 31.3, 9.8. N-(5-Chloroquinolin-8-yl)-3-methylbutanamide (3c). Yield 80%, 42 mg; white solid; mp 46-47 oC; Rf = 0.34; 1H NMR (400 MHz, CDCl3): δ 9.72 (s, 1 H), 8.82 (dd, J = 4.2, 1.6 Hz, 1 H), 8.73 (d, J = 8.4 Hz, 1 H), 8.53 (dd, J = 8.5, 1.6 Hz, 1 H), 7.60-7.51 (m, 2 H), 2.43 (d, J = 7.2 Hz, 2 H), 2.35-2.26 (m, 1 H), 1.07 (d, J = 6.6 Hz, 6 H); 13C NMR (100 MHz, CDCl3): δ 171.3, 148.6, 139.0, 133.9, 133.4, 127.3, 126.0, 124.1, 122.3, 116.4, 47.6, 26.4, 22.6; IR (KBr, cm-1): 3339, 2956, 1681, 1528, 1455, 1341, 1188, 1084, 925, 689, 552; HRMS (ESI): calcd for C14H16ClN2O[M+H]+ 263.0946, found 263.0938. N-(5-Chloroquinolin-8-yl)pentanamide (3d).17 Yield 80%, 42 mg ; white solid; mp 48-47 oC; Rf = 0.40; 1H NMR (400 MHz, CDCl3): δ 9.74 (s, 1 H), 8.82 (dd, J = 4.2, 1.6 Hz, 1 H), 8.72 (d, J = 8.4 Hz, 1 H), 8.53 (dd, J = 8.5, 1.6 Hz, 1 H), 7.64-7.51 (m, 2 H), 2.60-2.50 (m, 2 H), 1.87-1.73 (m, 2 H), 1.53-1.40 (m, 2 H), 0.98 (t, J = 7.3 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 171.9, 148.6, 138.9, 133.9, 133.4, 127.3, 125.9, 124.1, 122.3, 116.4, 38.0, 27.8, 22.5, 14.0. N-(5-Chloroquinolin-8-yl)octanamide (3e). Yield 53%, 32 mg; white solid; mp 53-54 oC; Rf = 0.50; 1H NMR (400 MHz, CDCl3): δ 9.65 (s, 1 H), 8.74 (dd, J = 4.2, 1.6 Hz, 1 H), 8.64 (d, J = 8.4 Hz, 1 H), 8.45 (dd, J = 8.5, 1.7 Hz, 1 H), 7.52-7.42 (m, 2 12


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H), 2.47 (t, J = 7.6 Hz, 2 H), 1.78-1.68 (m, 2 H), 1.38-1.17 (m, 8 H), 0.79 (t, 3 H); 13C NMR (100 MHz, CDCl3):δ 172.0, 148.6, 139.0, 134.0, 133.5, 127.4, 126.0, 124.1, 122.3, 116.4, 38.3, 31.8, 29.4, 29.2, 25.7, 22.7, 14.2; IR (KBr, cm-1): 3357, 2921, 1953, 1692, 1479, 1385, 1273, 1172, 956, 785, 670; HRMS (ESI): calcd for C17H22ClN2O[M+H]+ 305.1415, found 305.1407. N-(5-Chloroquinolin-8-yl)cyclohexanecarboxamide (3f).17 Yield 67%, 39 mg; white solid; mp 93-94 oC; Rf = 0.55; 1H NMR (400 MHz, CDCl3): δ 9.84 (s, 1 H), 8.84 (dd, J = 4.3, 1.6 Hz, 1 H), 8.74 (d, J = 8.4 Hz, 1 H), 8.55 (dd, 1 H), 7.61-7.52 (m, 2 H), 2.51-2.47 (m, 1 H), 2.08 (dd, J = 13.2, 1.6 Hz, 2 H), 1.92-1.87 (m, 2 H), 1.75-1.72 (m, 1 H), 1.69-1.57 (m, 2 H), 1.45-1.25 (m, 3 H);

13

C NMR (100 MHz,

CDCl3): δ 175.0. 148.6, 139.1,134.0, 133.6, 127.4, 126.1, 124.1, 122.4, 116.5, 47.0, 29.8, 25.9, 25.8. N-(5-Chloroquinolin-8-yl)benzamide (3g).8d Yield 66%, 37 mg; white solid; mp 139-141 oC; Rf = 0.60; 1H NMR (400 MHz, CDCl3): δ 10.67 (s, 1 H), 8.91-8.83 (m, 2 H), 8.58 (dd, J = 8.5, 1.6 Hz, 1 H), 8.07 (dd, J = 8.0, 1.6 Hz, 2 H), 7.64 (d, J = 8.4 Hz, 1 H), 7.62-7.51 (m, 4 H); 13C NMR (100 MHz, CDCl3): δ 165.6, 148.9, 139.5, 135.1, 134.0, 133.7, 132.1, 129.0, 127.5, 127.4, 126.2, 124.6, 122.6, 116.7. N-(5-Chloroquinolin-8-yl)-4-methylbenzamide (3h).8d Yield 63%, 37 mg; white solid; mp 133-134 oC; Rf = 0.58; 1H NMR (400 MHz, CDCl3): δ 10.65 (s, 1 H), 8.88 (d, J = 8.2 Hz, 1 H), 8.58 (dd, J = 8.2, 1.7 Hz, 1 H), 7.96 (d, J = 8.2 Hz, 2 H), 7.65 (d, J = 8.4 Hz, 1 H), 7.58 (dd, J = 8.5, 4.2 Hz, 1 H), 7.34 (d, J = 7.9 Hz, 2 H), 2.45 (s, 3

13



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H); 13C NMR (100 MHz, CDCl3): δ 165.6, 148.8, 142.7, 139.5, 134.2, 133.6, 132.2, 129.6, 127.5, 126.2, 124.5, 122.5, 116.6, 21.7. N-(5-Chloroquinolin-8-yl)-3-methylbenzamide (3i).8d Yield 74%, 39 mg; white solid; mp 71-72 oC; Rf = 0.50; 1H NMR (400 MHz, CDCl3): δ 10.62 (s, 1 H), 8.91-8.81 (m, 2 H), 8.56 (dd, J = 8.4, 1.5 Hz, 1 H), 7.91-7.80 (m, 2 H), 7.63 (d, J = 8.4 Hz, 1 H), 7.56 (dd, J = 8.5, 4.2 Hz, 1 H), 7.44-7.31 (m, 2 H), 2.47 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ 165.7, 148.8, 139.4, 138.8, 135.0, 134.0, 133.5, 132.9, 128.8, 128.2, 127.4, 126.1, 124.5, 124.3, 122.5, 116.6, 21.6. 2-Chloro-N-(5-chloroquinolin-8-yl)benzamide (3j). Yield 87%, 55 mg; white solid; mp 159-161 oC; Rf = 0.62; 1H NMR (400 MHz, CDCl3): δ 10.47 (s, 1 H), 8.89 (d, J = 8.4 Hz, 1 H), 8.83 (dd, J = 4.3, 1.7 Hz, 1 H), 8.56 (dd, J = 8.6, 1.8 Hz, 1 H), 7.82 (dd, J = 7.2, 2.2 Hz, 1 H), 7.65 (d, J = 8.4 Hz, 1 H), 7.56 (dd, J = 8.5, 4.2 Hz, 1 H), 7.50 (dd, J = 7.6, 1.8 Hz, 1 H), 7.47-7.36 (m, 2 H); 13C NMR (100 MHz, CDCl3): δ 164.9, 149.0, 139.4, 135.7, 133.9, 133.5, 131.8, 131.3, 130.7, 130.3, 127.4, 127.3, 126.1, 125.1, 122.6, 117.0; IR (KBr, cm-1) 3445, 3312, 1675, 1591, 1394, 1267, 743; HRMS (ESI): calcd for C16H11Cl2N2O[M+H]+ 317.0243, found 317.0235. 3-Chloro-N-(5-chloroquinolin-8-yl)benzamide (3k).8d Yield 33%, 21 mg; white solid; Rf = 0.60; mp 132-133 oC; 1H NMR (400 MHz, CDCl3): δ 10.64 (s, 1H), 8.91-8.90 (m, 1H), 8.84 (d, J = 8.4 Hz, 1H), 8.60 (d, J = 8.4 Hz, 1H), 8.04 (s, 1H), 7.93 (d J = 7.6 Hz, 1H), 7.66-7.55 (m, 3H), 7.49 (t, J = 8.0 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 164.1, 149.0, 139.4, 136.8, 135.2, 133.7, 132.7, 130.3, 127.8, 127.4, 126.2, 125.4, 125.0, 122.6, 116.8, 111.9. 14


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4-Chloro-N-(5-chloroquinolin-8-yl)benzamide (3l).8d Yield 72%, 45 mg; white solid; mp 119-120 oC; Rf = 0.58; 1H NMR (400 MHz, CDCl3): δ 10.62 (s, 1 H), 8.88 (dd, J = 4.2, 1.6 Hz, 1 H), 8.83 (d, J = 8.4 Hz, 1 H), 8.58 (dd, J = 8.5, 1.6 Hz, 1 H), 7.9 (d, J = 8.0 Hz, 2 H), 7.63 (d, J = 8.4 Hz, 1 H), 7.59 (dd, J = 8.0, 4.0 Hz, 1 H), 7.51 (d, J = 8.0 Hz, 2 H); 13C NMR (100 MHz, CDCl3): δ 161.4, 149.0, 141.6, 133.7, 132.0, 131.7. 129.5, 129.3, 129.0, 128.9, 127.5, 126.2, 122.6, 116.8. 3-Bromo-N-(5-chloroquinolin-8-yl)benzamide (3m). Yield 73%, 52 mg; white solid; mp 104 oC; Rf = 0.47; 1H NMR (400 MHz, CDCl3): δ 10.60 (s, 1 H), 8.89 (dd, J = 4.3, 1.6 Hz, 1 H), 8.82 (d, J = 8.4 Hz, 1 H), 8.57 (dd, J = 8.5, 1.6 Hz, 1 H), 8.18 (t, J = 1.8 Hz, 1 H), 7.96 (d, J = 8.0 Hz, 1 H), 7.71-7.69 (m, 1 H), 7.65-7.55 (m, 2 H), 7.41 (t, J = 8.0 Hz, 1 H);

13

C NMR (100 MHz, CDCl3): δ 163.9, 149.0, 139.3, 136.9, 135.1,

133.7, 133.6, 130.7, 130.5, 127.4, 126.1, 125.8, 125.9, 123.2, 122.6, 116.8; IR (KBr, cm-1):

3505,

3219,

1682,

1496,

1207,

698;

HRMS

(ESI):

calcd

for

C16H11BrClN2O[M+H]+ 360.9738, found 360.9728. N-(5-Chloroquinolin-8-yl)-4-fluorobenzamide (3n).8d Yield 74%, 44 mg; white solid; mp 154-156 oC; Rf = 0.57; 1H NMR (400 MHz, CDCl3): δ 10.63 (s, 1 H), 8.90 (dd, J = 4.3, 1.6 Hz, 1 H), 8.85 (d, J = 8.4 Hz, 1 H), 8.61 (dd, J = 8.4, 1.7 Hz, 1 H), 8.08 (dd, J = 8.4, 5.3 Hz, 2 H), 7.66 (d, J = 8.4 Hz, 1 H), 7.61 (dd, J = 8.5, 4.3 Hz, 2 H), 7.23 (t, J = 8.5 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 165.2 (d, J = 251.0 Hz), 164.4, 148.9, 139.3, 133.8, 133.7, 131.2 (d, J = 3.0 Hz), 129.8 (d, J = 9.3 Hz), 127.4, 126.2, 124.8, 122.6, 116.7, 116.0 (d, J = 21.9 Hz).

15



Page 16 of 23

N-(5-Chloroquinolin-8-yl)-2-phenylacetamide (3o). Yield 57%, 34 mg; white solid; mp 122-123 oC; Rf = 0.23; 1H NMR (400 MHz, CDCl3): δ 9.85 (s, 1 H), 8.74-8.66 (m, 2 H), 8.50 (dd, J = 8.4, 1.6 Hz, 1 H), 7.55 (d, J = 8.4 Hz, 1 H), 7.49 (dd, J = 8.5, 4.2 Hz, 1 H), 7.46-7.37 (m, 4 H), 7.35-7.31 (m, 1 H), 3.88 (s, 2 H); 13C NMR (100 MHz, CDCl3): δ 169.6, 148.7, 139.0, 134.6, 133.7, 129.7, 129.1, 127.5, 127.3, 126.0, 124.5, 122.3, 116.5, 45.5; IR (KBr, cm-1): 3322, 1689, 1492, 1379, 1219, 956, 719, 699; HRMS (ESI): calcd for C17H14ClN2O+[M+H]+ 297.0789, found: 297.0782. N-(5-Chloroquinolin-8-yl)-2-(3-methoxyphenyl)acetamide (3p). Yield 44%, 29 mg; white solid; mp 85-86 oC; Rf = 0.46; 1H NMR (400 MHz, CDCl3): δ 9.92 (s, 1 H), 8.74 (dd, J = 4.0, 1.6 Hz, 1 H), 8.70 (d, J = 8.0 Hz, 1H), 8.54 (dd, J = 8.0, 1.2 Hz, 1 H), 7.58 (d, J = 8.4 Hz, 1 H), 7.53 (dd, J = 8.5, 4.3 Hz, 1 H), 7.33 (t, J = 7.8 Hz, 1 H), 7.03-6.96 (m, 2 H), 6.88 (dd, J = 8.3, 2.4 Hz, 1 H), 3.86 (s, 2 H), 3.83 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ 169.5, 160.3, 148.6, 139.0, 136.1, 133.7, 130.2, 127.4, 126.1, 124.6, 122.4, 122.0, 116.7, 115.1, 113.4, 55.4, 45.6; IR (KBr, cm-1) 2917, 1684, 1585, 1526, 1485, 1305, 1261; HRMS (ESI): calcd for C18H16ClN2O2[M+H]+ 327.0895, found 327.0885. 2-(4-Chlorophenyl)-N-(5-chloroquinolin-8-yl)acetamide (3q). Yield 50%, 33 mg; white solid; mp 141-142 oC; Rf = 0.15; 1H NMR (400 MHz, CDCl3): δ 9.84 (s, 1 H), 8.75 (dd, J = 4.2, 1.7 Hz, 1 H), 8.67 (d, J = 8.4 Hz, 1 H), 8.53 (dd, J = 8.5, 1.6 Hz, 1 H), 7.60- 7.51 (m, 2 H), 7.36 (d, J = 1.1 Hz, 4 H), 3.85 (s, 2 H); 13C NMR (100 MHz, CDCl3):δ 169.0, 148.8, 139.0, 133.6, 133.5, 133.1, 131.0, 129.2, 127.3, 126.0, 124.7,

16


Page 17 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


122.4, 116.5, 44.6; IR (KBr, cm-1): 3352, 1686, 1529, 1424, 1320, 1092, 961, 932, 761; HRMS (ESI): calcd for C17H13Cl2N2O[M+H]+: 331.0399, found 331.0390. N-(5-Chloroquinolin-8-yl)thiophene-2-carboxamide (3r).8d Yield 52%, 30 mg; white solid; mp 134-135 oC; Rf = 0.25; 1H NMR (400 MHz, CDCl3): δ 10.52 (s, 1 H), 8.89 (dd, J = 4.3, 1.6 Hz, 1 H), 8.78 (d, J = 8.4 Hz, 1 H), 8.58 (dd, J = 8.5, 1.5 Hz, 1 H), 7.83 (dd, J = 3.7, 1.1 Hz, 1 H), 7.69-7.47 (m, 3 H), 7.23-7.13 (m, 1 H); 13C NMR (100 MHz, CDCl3): δ 160.1, 148.9, 139.9, 139.1, 133.7, 133.6, 131.3, 128.7, 128.0, 127.5, 126.2, 124.7, 122.6, 116.6. N-(5-Chloro-6-methylquinolin-8-yl)-4-methylbenzamide (3s). Yield 80%, 50mg; white solid; mp 141-142 oC; Rf = 0.34; 1H NMR (400 MHz, CDCl3): δ 10.61 (s, 1 H), 8.87 (s, 1 H), 8.81 (dd, J = 4.3, 1.5 Hz, 1 H), 8.58 (dd, J = 8.5, 1.6 Hz, 1 H), 7.96 (d, J = 8.0 Hz, 2 H), 7.54 (dd, J = 8.5, 4.2 Hz, 1 H), 7.34 (d, J = 7.9 Hz, 2 H), 2.63 (s, 3 H), 2.45 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ 165.5, 147.7, 142.6, 138.3, 135.5, 133.3, 132.3, 129.6, 127.4, 126.3, 123.3, 122.5, 119.4, 21.7, 21.3; IR (KBr, cm-1): 3471, 2951, 1609, 1577, 1375, 1208, 1039, 823, 795; HRMS (ESI): calcd for C18H15ClN2NaO [M+H]+ 333.0765, found 333.0767. N-(5-Bromoquinolin-8-yl)propionamide (3t).6b Yield 52%, 29 mg; white solid; mp 74-75 oC; Rf = 0.30; 1H NMR (400 MHz, CDCl3): δ 9.80 (s, 1 H), 8.82 (dd, J = 4.3, 1.6 Hz, 1 H), 8.69 (d, J = 8.4 Hz, 1 H), 8.53 (dd, J = 8.5, 1.6 Hz, 1 H), 7.79 (d, J = 8.4 Hz, 1 H), 7.57 (dd, J = 8.5, 4.2 Hz, 1 H), 2.60 (q, J = 7.6 Hz, 2 H), 1.34 (t, J = 7.6 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 172.7, 148.7, 139.2, 136.2, 134.6, 131.1, 127.3, 122.8, 117.1, 114.1, 31.4, 9.8. 17



Page 18 of 23

Procedure for the synthesis of product 3u

The the i-pentoyl chloride (0.4 mmol) and NaI (0.48 mmol) were employed in a sealed round bottom flask stirred for 10 min at rt. When the acyl chlorides completely converted into acyl iodides, the colourless reaction mixtures were turned to dark yellow.1 The 8-aminoquinoline 1 (0.2 mmol), CuO (0.08 mmol) and xylene (2 mL) were then added to the vessel. The expected product 3t was acquired by subsequent treatment following the procedure in the synthesis of 3a-3t. N-(5-Iodoquinolin-8-yl)-3-methylbutanamide (3u). Yield 42%, 30 mg; white solid; mp 71-72 oC; Rf = 0.33; 1H NMR (400 MHz, CDCl3): δ 9.75 (s, 1 H), 8.85 (dd, J = 4.3, 1.6 Hz, 1 H), 8.75 (d, J = 8.5 Hz, 1 H), 8.57 (dd, J = 8.5, 1.7 Hz, 1 H), 7.62-7.54 (m, 2 H), 2.44 (d, J = 7.2 Hz, 2 H), 2.37-2.24 (m, 1 H), 1.07 (d, J = 6.6 Hz, 6 H); 13C NMR (100 MHz, CDCl3): δ 171.5, 148.7, 133.9, 133.7, 127.4, 126.1, 124.2, 122.4, 116.6, 47.6, 26.4, 22.7; IR (KBr, cm-1): 3391, 1751, 1621, 1351, 1107, 856, 719; HRMS (ESI): calcd for C14H16IN2O+[M+H]+ 355.0302, found 355.0292. Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: the 1H/13C NMR spectra of all products. AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected] (J.-P.W.). *E-mail: [email protected] (Y.L.). Notes 18


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The authors declare no competing financial interest.

ACKNOWLEDGEMENTS

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the Dual Role of Acyl Halides - ACS Publications

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