16 chapter 3 3 -...

Alum catalyzed one-pot solvent-free synthesis of

amidoalkyl naphthols under ultrasound irradiation

110

3.3.1 Introduction

Multicomponent reactions have attracted a considerable attention in

organic synthesis as they can produce the target products in a single operation

without isolating the intermediates and thus reducing the reaction times and

energy.1-4 In the past decades, the development of effective multicomponent based

synthesis has played an important role to achieve high atom economy and

sustainable chemistry. The challenge is to conduct an MCR in such a way that the

network of pre-equilibrated reactions channel into the main product and do not

yield side products. The result is clearly dependent on the reaction conditions

such as solvent, temperature, catalyst, concentration, kind of starting materials

and functional groups. Such considerations are of particular importance in

connection with the design and discovery of novel MCRs. There has been

tremendous development in three or four component reaction specially Biginelli,5

Ugi,6 Passerini,7 Mannich8 reactions, which have further led to renaissance of

MCRs. Nevertheless, great efforts have been and still are being made to find and

develop new MCRs.

Compounds bearing 1,3-amino-oxygenated functional moiety are common

in a variety of biologically important natural products and potent drugs, including

a number of nucleosides, antibiotics and HIV protease inhibitors, such as ritonavir

and lipinavir.9 Even hypotensive and bradycardiac effects of these compounds

have been evaluated.10 It is noteworthy that aminotetralin derivatives manifest a

number of important and therapeutically useful biological activities such as

antidepressant and antitumor.11 Literature survey showed that aminonaphthols

have been reported to exhibit antihypertensive, adrenoceptor blocking and Ca2+

channel blocking activities. 1-Pyrrolidinylmethyl-2-naphthol hydrochloride (TPY-

β) (I, Figure 1) has been shown to produce a reduction in blood pressure (BP) and

heart rate (HR) in anaesthetized rats. The ionic mechanism of the cardiovascular

activity of TPY- β has also been examined. TPY- β involves a direct depressant

action on heart cells and vascular smooth cells.

Shen et al.12 observed that a series of 1-alkylaminomethylnaphthols (II,

Figure 1) showed hypotensive and bradycardiac effects in normotensive rats. They



111

also exhibited in vitroinotropic and aortic contraction effects in isolated rat left

atria and aorta.12

O

+NH

CH3

OH

R2

N

R1

Cl-

I II

Figure 1. Structure of TPY-β (I) and 1-alkylaminomethylnaphthol (II).

A higher depressor and bradycardiac activity was found for compounds

substituted on nitrogen by naphthol with amines. These compounds produced

biphasic changes in contractile force in isolated rat atria, which was correlated to

blood pressure and heart rate activity. The biological activity of these compounds

can be explained in terms of substitution on nitrogen. The development of N-

substituted-1-aminomethyl-2-naphthols with duel effects would be of potential

therapeutic advantage, which in turn can be synthesized from amidoalkyl

naphthols. Despite this broad range of applications, only a few members of this

family of compounds have been reported. The development of new methods for

their assembly is therefore of considerable synthetic importance.

The preparation of 1-amidoalkyl-2-naphthols can be carried out by

multicomponent condensation of β-naphthol, aryl aldehydes and acetonitrile or

amides in the presence of acid catalysts such as Ce(SO4)2,13 p-TSA,14

montmorillonite K 10 clay,15 iodine,16 sulfamic acid,17 cation-exchanged resins,18

silica sulphuric acid (SSA),19 zirconyl(IV) chloride,20 K5CoW12O40·3H2O,21

FeCl3·SiO2,22 Sr(OTf)3,23 NaHSO4·H2O,24 HClO4·SiO2,25 FeH(SO4)2,26 Al(H2PO4)3,27

PPA·SiO2,28 H3Mo12O40P,29 HPA,30 P2O531 and 2,4,6-trichloro-1,3,5-triazine.32

In recent years, several improved procedures have been reported for the

synthesis of amidoalkyl naphthols.

Shaterian et al.33 reported synthesis of amidoalkyl naphthols using silica

supported sodium hydrogen sulphate as heterogeneous catalyst under a thermal

solvent-free conditions (Scheme 1).

Shaterian et al. Turk. J. Chem. 2009, 33, 449



112

Scheme 1. Reaction conditions: (i) CH3CONH2, NaHSO4·SiO2, solvent-free, 125 ºC,

5-45 min, 67-95%.

Khabazzadeh et al.34 have developed a protocol for the synthesis of

amidoalkyl naphthols using Cu-exchanged heteropoly acids. This protocol gives

valuable results though with some limitations such as long reaction time and low

yields (Scheme 2).

Khabazzadeh et al. J. Chem. Sci. 2009, 121, 429

Scheme 2. Reaction conditions: (i) Heteropoly salt, TBAB, 100 ºC, 90 min, 70-95%.

Lei et al.35 have reported practical procedure for the synthesis of amidoalkyl

naphthols using thiamine hydrochloride (VB1) in excellent yields. The salient

features of the catalyst are efficiency, inexpensive, non-toxicity and metal ion free

(Scheme 3).

Lei et al. Tetrahedron Lett. 2009, 50, 6393

Scheme 3. Reaction conditions: (i) Thiamine hydrochloride, EtOH, 80 ºC, 4 h, 75-93%.

Shingare et al.36 have describe an efficient and easy method for synthesis of

amidoalkyl naphthols by the condensation of aromatic/heteroaromatic/ aliphatic

aldehydes, 2-naphthol and amides or urea under thermal condition at 60 ºC in the



113

presence of acidic ionic liquid 1-n-butyl-3-methylimidazolium hydrogen sulphate

([bmim]HSO4) (Scheme 4).

Shingare et al. Bull. Korean Chem. Soc. 2009, 30, 2887

Scheme 4. Reaction conditions: (i) [bmim]HSO4, 60 °C, 30-50 min, 80-96%.

Hajipour et al.37 reported a method for the preparation of amidoalkyl

naphthols from condensation of aldehydes with amides or urea and 2-naphthol in

the presence of a catalytic amount of Brønsted acidic ionic liquid ([TEBSA][HSO4])

under thermal solvent-free conditions (Scheme 5).

Hajipour et al. Tetrahedron Lett. 2009, 50, 5649

Scheme 5. Reaction conditions: (i) 5 mol% IL, 120 °C, 10 min, 73-90%.

The English word “alum” is derived, as is stated by various reference

books, from Latin word alumen. The origin of the latter word is unknown.

Attempts to trace it back to certain Greek words meaning ‘salt’ or ‘brine’ have not

found favor for the Greek equivalent of alumen was stypteria. From the Latin the

word found its way into modern European languages: alum in English, alun in

French and alaun in Germeny, etc.38

Alum was imported into England mainly from the Middle East and from

the 15th century onwards, the Papal States for hundreds of years. Its use there was

as a dye-fixer (mordant) for wool (which was one of England's primary

industries), the value of which increased significantly if dyed. In the 17th century

an industry was founded in Yorkshire to process the shale which contained the

key ingredient, aluminium sulfate and made an important contribution to the



114

Industrial Revolution. Alum (known as turti in local Indian languages) was also

used for water treatment by Indians for hundreds of years.

Alum is a salt that in chemistry is a combination of alkali metals, such as

sodium, potassium or ammonium and trivalent metals, such as aluminum, iron or

chromium. The most common form potassium aluminum sulfate or potash alum

is one form that has been used in food processing. Alum refers to a specific

chemical compound and a class of chemical compounds. The specific compound is

the hydrated aluminum potassium sulfate with the formula KAl(SO4)2·12H2O.

Alums are useful for a range of industrial processes. They are soluble in water,

have an astringent, acid and sweetish taste; react acid to litmus. Their unique

properties as mild organic Lewis acid and their mitigated reactivity profile

coupled with their stability, non-toxic, reusable, inexpensive, easily available and

ease of handling makes alum a particular attractive class of synthetic reagent.

Azizian et al.39 found that alum is an efficient catalyst for the stereoselective

one-pot three-component cyclocondensation of homophthalic anhydride,

aldehydes and amines under mild conditions to afford the corresponding cis-

isoquinolonic acids in good yields. In this direction, the use of a alum is relatively

nontoxic and inexpensive. In the course of his research on application of alum in

organic reactions, He found that alum was an effective promoter in the

preparation of cis-isoquinolonic acids (Scheme 6).

Azizian et al. J. Org. Chem. 2005, 70, 350

Scheme 6. Reaction conditions: (i) Alum, CH3CN, rt, 6-9 h, 81-91%.

Dabiri et al.40 have been used alum [KAl(SO4)2·12H2O] as an efficient

catalyst in a one-pot three-component cyclocondensation of isatoic anhydride and

primary amines or ammonia sources such as (NH4)2CO3, NH4OAc and NH4Cl

with aromatic aldehydes under mild conditions to afford the corresponding



115

mono- and disubstituted 2,3-dihydroquinazolin-4(1H)-ones in good yields

(Scheme 7).

Dabiri et al. Tetrahedron Lett. 2005, 46, 6123

Scheme 7. Reaction conditions: (i) Alum, H2O or EtOH, reflux, 1-5 h, 79-92%;

(ii) Alum, EtOH, reflux, 4-6 h, 69-83%.

Azizian et al.41 also synthesized 3,4-dihydropyrimidin-2(1H)-one

derivatives in moderate to high yields in one-pot three component reaction from

the corresponding aldehydes, ketones or 1,3-dicarbonyl compounds and urea in

the presence of catalytic amount of KAl(SO4)2·12H2O (alum) supported on silica

gel (alum-SiO2) as a non-toxic, reusable, inexpensive and easily available reagent

under solvent-free conditions at 80 °C. Compared to the classical Biginelli reaction,

this new method consistently has the advantage of good yields (Scheme 8).

Azizian et al. Appl. Catal. A-Gen. 2006, 300, 85

Scheme 8. Reaction conditions: (i) Alum·SiO2, 80 ºC, 88-93%.

Dabiri et al.42 have been used alum [KAl(SO4)2·12H2O] as an efficient

catalyst in the Pechmann condensation of phenol derivatives with β-keto esters

leading to the formation of coumarins in excellent yields under solvent-free

conditions (Scheme 9).

Dabiri et al. Monatsh. Chem. 2007, 138, 997



116

Scheme 9. Reaction conditions: (i) Alum (40 mol%), solvent-free, 80 ºC, 2-3 h, 80-95%.

Kapoor et al.43 reported alum catalyzed synthesis of 1,5-benzodiazepines in

good to excellent yields from the condensation of 1 mole of o-phenylenediamines

with 2 moles of ketones under solvent-free conditions (Scheme 10).

Kapoor et al. Aust. J. Chem. 2008, 61,159

Scheme 10. Reaction conditions: (i) Alum, solvent-free, 80 ºC, 74-91%.

Mohammadi et al.44 reported synthesis of some new 4(3H)-quinazolinones

using alum [KAl(SO4)2·12H2O] as an efficient and recyclable heterogeneous

catalyst under microwave irradiation (Scheme 11).

Mohammadi et al. J. Appl. Chem. Res. 2008, 6, 55

Scheme 11. Reaction conditions: (i) Alum, MW (385 W), 6 min, 81-93%.

Shingare et al.45 reported alum catalyzed simple and efficient synthesis of

bis(indolyl)methanes by ultrasound approach by the reaction of 1H-indole with

various aldehydes/ketones. The remarkable advantages of this method are simple

experimental procedure and shorter reaction times (Scheme 12).


Scheme 12. Reaction conditions: (i) Alum, solvent-free, ultrasound irradiation, 10-30 min,

71-95%.



117

Shingare et al.46 have described efficient synthesis of quino[2,3-

b][1,5]benzoxazepine α-aminophosphonate derivatives by the nucleophilic

addition of triethyl phosphite to substituted quino[2,3-b][1,5]benzoxazepines

promoted by alum [KAl(SO4)2·12H2O] (Scheme 13).


Scheme 13. Reaction conditions: (i) Alum (20 mol%), solvent-free, rt, 20-25 min, 80-90%.

Sandhu et al.47 reported alum catalyzed one-pot synthesis of α–amino

nitriles (Scheme 14).

Sandhu et al. RASAYAN J. Chem. 2009, 2, 182

Scheme 14. Reaction conditions: (i) Alum, CH3CN, rt, 45-80 min, 79-94%.

Sandhu et al.48 reported alum catalyzed solvent-free method for

Knoevenagel reaction with excellent yields. The use of a green catalyst, solvent-

free conditions and shorter reaction times are the main features of this efficient

protocol (Scheme 15).

Sandhu et al. Green Chem. Lett. Rev. 2009, 2, 189

Scheme 15. Reaction conditions: (i) Alum, solvent-free, rt, 5-10 min, 85-95%.

Shingare et al.49 have described synthesis of 5-arylidine-2,4-

thiazolidinediones by the Knoevenagel condensation of aromatic aldehydes with

2,4-thiazolidinedione in aqueous media at 90 ºC using alum as an inexpensive,

efficient and non-toxic catalyst. This method affords the 5-arylidine-2,4-



118

thiazolidinediones in short reaction times, high yields and green aspects by

avoiding toxic catalysts and hazardous solvents (Scheme 16).

Shingare et al. Green Chem. Lett. Rev. 2010, 3, 17

Scheme 16. Reaction conditions: (i) Alum (10 mol%), H2O, 90 ºC, 50-90 min, 85-95%.

Recently, Madje et al.50 reported synthesis of anthraquinone derivatives

from phthalic anhydride and substituted benzenes in the presence of alum as an

catalyst. The remarkable advantages of this method are use of inexpensive and

easily available catalyst, mild reaction conditions and shorter reaction times

(Scheme 17).

Madje et al. Green Chem. Lett. Rev. 2010, 3, 269

Scheme 17. Reaction conditions: (i) Alum (25 mol%), H2O, rt, 60-120 min, 70-96%.



119

3.3.2 Present work

In view of the importance of amidoalkyl naphthols due to its

pharmacological properties and its interesting reactivity, several methods were

reported for its synthesis. Most of the method leading to synthesis of amidoalkyl

naphthols involves the use of solvents along with acid catalysts. Most of the

methods were carried out at reflux temperature in organic solvents for a longer

period. The use of organic solvents gives rise to one of the most abundant sources

of chemical waste in the fine chemicals and pharmaceutical industry and causes

detrimental effects on the environment as well as human health. These processes

also generate waste containing both catalyst and solvent, which have to be

recovered, treated and disposed of. Consequently, the methods that successfully

minimize their use are the focus of much attention.

In present work, we reported a new and efficient method for the synthesis

of amidoalkyl naphthols using a catalytic amount of alum under the influence of

ultrasound irradiation at room temperature under solvent-free conditions

(Scheme 18).

Scheme 18. Alum catalyzed synthesis of amidoalkyl naphthols under ultrasound

irradiation.



120

3.3.3 Results and discussion

Ultrasound irradiation has been established as an important technique in

synthetic organic chemistry. It has been used as an efficient heating source for the

reactions. Shorter reaction time is main advantage of ultrasound-assisted reactions

(for more details see chapter 1).

Initially, to optimize the reaction conditions, we carried out the reaction of

β-naphthol (1 mmol) with benzaldehyde (1 mmol) and acetamide (1.2 mmol) as a

model reaction in the presence of different amounts of catalyst under the influence

of ultrasound irradiation. The catalytic activity of alum was investigated with

respect to the catalyst loading (Table 1). Many experiments were carried out on a

model reaction under similar conditions. We found that when less than 5 mol% of

catalyst (alum) was applied; it resulted in lower yield of the product (Entry 2,

Table 1). Whereas, use of more than 5 mol% of catalyst, did not improve the yield

(Entries 4~5, Table 1). The use of 5 mol% of catalyst resulted in highest yield

(Entry 3, Table 1). To illustrate the need of the alum, a model reaction was

conducted in the absence of catalyst; the yield of product in this case was only 18%

after 45 min (Entry 1, Table 1). Hence, alum is an important component of the

reaction.

Table 1. Effect of catalyst concentration on model reactiona (4a)

Entry Alum (mol%) Time (min) Yieldb (%)

1 0 45 18c

2 2.5 10 84

3 5 10 91

4 7.5 10 90

5 10 10 91 a Reaction conditions: β-naphthol (1 mmol), benzaldehyde (1 mmol) and

acetamide (1.2 mmol), ultrasound irradiation at room temperature. b Yield of pure, isolated product. c Absence of catalyst, under ultrasound irradiation for 45 min.

To establish the generality and scope of our method, we applied the

optimized protocol to a diverse range of aryl aldehydes with acetamide/urea and

β-naphthol (Table 2). As seen, the reactions proceeded efficiently and respective

amidoalkyl naphthols were obtained in good to excellent yields. The effect of



121

electron-withdrawing and electron-donating substituents on the aromatic ring of

aryl benzaldehydes on the reaction was investigated. As expected, the aryl

aldehydes with electron-withdrawing groups reacted faster than aryl aldehydes

having electron-donating groups. We also carried out reactions using urea instead

of acetamide and could synthesize eight more amidoalkyl naphthols in good

yields (Entries 8~15, Table 2). Aliphatic aldehyde reacted sluggishly and gives

side product (Entry 16, Table 1).

Table 2. Alum catalyzed synthesis of amidoalkyl naphthols (4a- 4p)

Entry R1 R2 Producta Time (min)

Yieldb

(%)

1 C6H5 CH3 4a 10 91, 78c, 0d

2 4-MeC6H4 CH3 4b 15 88

3 4-OMeC6H4 CH3 4c 13 86

4 4-ClC6H4 CH3 4d 10 90

5 4-NO2C6H4 CH3 4e 8 95

6 2-ClC6H4 CH3 4f 14 89

7 2-NO2C6H4 CH3 4g 15 92

8 C6H5 NH2 4h 10 93

9 4-OHC6H4 NH2 4i 12 89

10 4-MeC6H4 NH2 4j 14 86

11 4-OMeC6H4 NH2 4k 12 85

12 4-ClC6H4 NH2 4l 12 92

13 4-NO2C6H4 NH2 4m 10 94

14 2-ClC6H4 NH2 4n 15 90

15 2-NO2C6H4 NH2 4o 13 94

16 CH3CH2 CH3 4p 20 25 a All products were characterized by IR, 1H NMR, 13C NMR spectroscopic and EA data and their

m.p. compared with literature values.13-37 b Yield of pure, isolated product. c For non-sonicated thermal solvent-free experiment: β-naphthol (1 mmol), benzaldehyde (1

mmol), acetamide (1.2 mmol) and alum (5 mol%) was stirred at 80 °C for 25 min. d For non-sonicated experiment: β-naphthol (1 mmol), benzaldehyde (1 mmol), acetamide

(1.2 mmol) and alum (5 mol%) was stirred for 30 min at room temperature, no product was detect in the absence of ultrasound irradiation.



122

Based on the results of this study, it seems that the ultrasound irradiation

procedure improves the reaction times and yields than the purely thermal

procedures. The reaction of β-naphthol with aryl aldehydes in the presence of an

acid catalyst is known to give ortho-quinone methides (o-QMs).22 The same

o-QMs, generate in situ, have been reacted with acetamide/urea via conjugate

addition to form amidoalkyl naphthols (Scheme 19).

Scheme 19. Suggested mechanism for the preparation of amidoalkyl naphthols (4a-4p).

To show the merit of present work in comparison with reported results in

the literature,13,14,16,20,24 as shown in Table 3, alum under the influence of

ultrasound irradiation can act as an effective catalyst with respect to reaction times

and yields. Thus, the present protocol with alum as a catalyst is superior to the

reported catalytic methods.

Table 3. Comparison of result with reported procedure for synthesis of

amidoalkyl naphthol (4a)

Entry Catalyst Conditions Time Yielda (%)

1 Ce(SO4)2 (100 mol%) CH3CN, reflux 36 h 72

2 p-TSA (10 mol%) Solvent-free, 125 °C 5 h 88

3 I2 (5 mol%) Solvent-free, 125 °C 5 h 85

4 ZrOCl2· 8H2O (0.1 mmol) ClCH2CH2Cl, rt 14 h 86

5 NaHSO4· H2O (45 mg) Solvent-free, 120 °C 11 min 86

6 Alum (5 mol%) Solvent-free, ))) 10 min 91 a Yield of pure, isolated product.



123

3.3.4 Conclusions

In summary, we have discovered a novel and efficient protocol for the

synthesis of amidoalkyl naphthols by multicomponent condensation of β-

naphthol, aryl aldehydes and acetamide/urea in the presence of alum under

ultrasound irradiation. The main advantages of this method are simple

experimental procedure, short reaction times, mild and solvent-free reaction

conditions and use of inexpensive, nontoxic and easily available catalyst.



124

3.3.5 Experimental

3.3.5.1 General procedure for the synthesis of amidoalkyl naphthols

A mixture of β-naphthol 1 (1 mmol), aldehyde 2 (1 mmol), acetamide/urea

3 (1.2 mmol) and alum (5 mol%) was irradiated in the water bath of an ultrasonic

cleaner for the appropriate time (Table 2). The reaction was monitored by TLC.

After completion of the reaction, the reaction mixture was poured into ice-cold

water and stirred for 5 min. The resulting solid product was filtered and

recrystallized from EtOH:H2O (1:3) to afford the pure product.

3.3.5.2 Characterization data for some representative compounds (4d, 4e, 4i, 4l)

N-((4-chlorophenyl)(2-hydroxynaphthalen-1-yl)methyl)acetamide (4d)

Nature : Solid

Melting point : 225-226 ºC (lit.13 m.p. 224-227 ºC)

Yield : 90%

IR (KBr, cm-1) : 1629, 3055, 3390.

1H NMR

(300 MHz, CDCl3)

: δ = 1.98 (s, 3H), 7.00-7.36 (m, 8H), 7.77 (m, 3H),

8.46 (bs, 1H), 10.01 (bs, 1H).

13C NMR

(75 MHz, CDCl3)

: δ = 22.59, 47.30, 118.23, 122.27, 122.96, 127.70,

128.24, 128.40, 129.29, 130.39, 132.00, 141.56,

152.94, 169.16.

Elemental analysis

:

C19H16ClNO2

Calcd. C 70.05, H 4.95, N 4.30%.

Found C 70.12, H 4.82, N 4.42%.



125

N-((2-hydroxynaphthalen-1-yl)(4-nitrophenyl)methyl)acetamide (4e)

Nature : Solid


Yield : 95%

IR (KBr, cm-1) : 1350, 1521, 1639, 3053 (br), 3390.

1H NMR (300 MHz, CDCl3,

Figure 2, Page no. 127)

: δ = 2.06 (s, 3H), 6.7 (bs, 1H), 7.24 (m, 3H), 7.35-

7.44 (m, 3H), 7.76 (m, 2H), 7.84 (s, 1H), 8.10 (d, J

= 8.5 Hz, 2H), 10.24 (bs, 1H).

13C NMR (75 MHz, CDCl3,


: δ = 30.35, 44.00, 117.77, 118.39, 122.55, 123.09,

126.68, 127.04, 128.60, 129.81, 132.14, 145.83,

151.00, 153.30, 169.86, 172.00.

Elemental analysis

:

C19H16N2O4

Calcd. C 67.85, H 4.79, N 8.33%.

Found C 67.81, H 4.73, N 8.35%.

1-((2-hydroxynaphthalen-1-yl)(4-hydroxyphenyl)methyl)urea (4i)

Nature : Solid

Melting point : 224-225 ºC (lit.17 m.p. 223-224 °C)

Yield : 89%

IR (KBr, cm-1) : 1720, 3146, 3246.



126

1H NMR (300 MHz, CDCl3,


: δ = 5.94 (s, 1H), 6.60-6.80 (m, 3H), 7.06-7.12 (m,

3H), 7.25 (d, J = 8.7 Hz, 1H), 7.32-7.48 (m, 3H),

7.65 (d, J = 8.2 Hz, 1H), 7.70-7.90 (m, 3H), 8.60

(bs, 1H).

13C NMR (75 MHz, CDCl3,


: δ = 53.41, 114.50, 115.10, 115.98, 123.18, 124.94,

127.25, 128.14, 128.47, 128.79, 129.68, 130.25,

133.42, 147.24, 149.34, 157.12.

Elemental analysis

:

C18H16N2O3

Calcd. C 70.12, H 5.23, N 9.09%.

Found C 70.21, H 5.58, N 8.98%.

1-((4-chlorophenyl)(2-hydroxynaphthalen-1-yl)methyl)urea (4l)

Nature : Solid


Yield : 92%

IR (KBr, cm-1) : 1749, 3147, 3246.

1H NMR

(300 MHz, CDCl3)

: δ = 3.4 (s, 2H), 5.95 (m, 2H), 6.13 (bs, 1H), 6.71-

6.85 (m, 3H), 7.34-7.47 (m, 3H), 7.79 (d, J = 7.9

Hz, 1H), 7.94 (m, 2H), 8.82 (bs, 1H).

13C NMR

(75 MHz, CDCl3)

: δ = 53.41, 101.50, 107.27, 108.40, 113.80, 116.64,

120.25, 122.94, 124.87, 127.15, 128.68, 130.17,

136.60, 146.66, 147.34, 149.04.

Elemental analysis

:

C18H15ClN2O2

Calcd. C 66.16, H 4.63, N 8.57%.

Found C 66.22, H 4.69, N 8.64%.

Alum catalyzed one-pot solvent-free synthesis of amidoalkyl naphthols under ultrasound irradiation

129

Figure 2. 1H NMR spectra of N-((2-hydroxynaphthalen-1-yl)(4-nitrophenyl)methyl)acetamide (4e).

127

OH

NHCOCH3

O2N


130

Figure 3. 13C NMR spectra of N-((2-hydroxynaphthalen-1-yl)(4-nitrophenyl)methyl)acetamide (4e).

128

OH

NHCOCH3

O2N


131

Figure 4. 1H NMR spectra of 1-((2-hydroxynaphthalen-1-yl)(4-hydroxyphenyl)methyl)urea (4i).

129


132

Figure 5. 13C NMR spectra of 1-((2-hydroxynaphthalen-1-yl)(4-hydroxyphenyl)methyl)urea (4i).

130



131

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