Synthesis of Î±-Amino Phosphonates under a Neat Condition

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Synthesis of #-amino phosphonates under a neat condition catalyzed by multiple-acidic ionic liquids Anguo Ying, Shuo Liu, Jianguo Yang, and Huanan Hu Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/ie5025062 • Publication Date (Web): 25 Sep 2014 Downloaded from http://pubs.acs.org on September 28, 2014

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Industrial & Engineering Chemistry Research

Synthesis of α-amino phosphonates under a neat condition catalyzed by multiple-acidic ionic liquids Anguo Ying a *, Shuo Liu b, Jianguo Yang a, Huanan Hu a (a School of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou 318000, PR China) (b College of Chemistry, Nankai University, Tianjin 300071, PR China)

Abstract: A simple and efficient method for the synthesis of α-amino phosphonates has been accomplished from aromatic aldehydes, diethyl phosphite, and aromatic amines using multiple-acidic ionic liquids catalysts under solvent free condition at room temperature and these compounds were characterized by H-H COSY. Key words: α-amino phosphonate, multiple-acidic ionic liquids, H-H COSY

Introduction α-Amino phosphonates are an important class of compounds widely used in biochemical and pharmaceutical chemistry due to their structural analogy to α-amino acids and transition state mimics of peptide hydrolysis.[1] Three-component synthesis starting from aldehydes, amines and diethyl phosphite or triethyl phosphite have been reported catalyzed by Lewis and Bronsted acid, such as HCl or H2SO4[2],AlCl3[3], InCl3[4], BF3·Et2O[5], LiClO4[6], SbCl3/Al2O3[7], Sulfamic acid[8], H3BO3[9], FeCl3 and CuCl2[10], tartaric acid[11], and other methods[12]. However, many of these methods suffer from some drawbacks such as long reaction times, low yields of the products,

* Corresponding authors. Tel/fax: +86 576 88660359. E-mail address: [email protected] or [email protected] (A. Ying) 1

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requiring stoichiometric amounts of catalysts, use of toxic solvents, and high cost. What’s more, water formed during imine formation can decompose or deactivate these moisture sensitive Lewis and BrØnsted acids and hence difficult to handle. Recently, ionic liquids, due to their interesting properties, have been turned to be a kind of promising alternative medium/catalysts for various chemical processes[13]. Yadav[14] et al. used [bmim][BF4] and [bmim][PF6] as catalysts for the synthesis of α-aminophosphonates. Akbari[15] et al. used imidazolium based ionic liquid [bsmim][CF3SO3] and Sadaphal[16] et al. used [bnmim][HSO4] as the recyclable catalyst for the synthesis of α-aminophosphonates, Fang[17] et al. synthesized a series of SO3H-functionalized ‘halogen-free’ ionic liquids and used them as catalysts for the synthesis of α-aminophosphonates in water. Since α-amino phosphonate derivatives are increasingly important in pharmaceuticals and industry, the development of simple, eco-friendly, low cost protocols are still desirable. Recently, our group synthesized a series of novel SO3H-Functionalized Hydroxy-Ethyl Amine ionic liquids, [SFHEA][X] (Fig. 1), as catalysts for the Henry reaction of versatile aldehydes and nitroalkane under solvent-free conditions[18]. As multiple-acidic ionic liquids, [SFHEA][X] will be potential catalysts for the synthesis of α-aminophosphonates. In continuation of our investigations of their further application for other organic transformations, herein we successfully endeavor yet another application of these ionic liquids as catalysts for the synthesis of α-aminophosphonates under mild condition. The reactions preceded smoothly affording target products in good to excellent yields within hours. The procedure offered several advantages including short reaction time, good yields, easy workup procedures and without using of metal catalysts. What’s more, the catalyst could be reused up to five times, still maintaining a high catalytic activity. In conclusion, it is a green and efficient

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surrogate for synthesis of α-amino phosphonates.

Fig. 1 Structure of [SFHEA][X] Experimental section General. All chemicals were used as supplied without further purification unless otherwise specified. Melting points were taken on a Gallenkamp melting point apparatus. 1H, 13C NMR and H-H COSY spectra were recorded on a Bruker AM-400 MHz spectrometer. HRMS values were measured by a JEOL JMS-SX or JEOL JMS-SX 102A spectrometer. Flash column chromatography was performed on silica gel (200–300 mesh) (Qingdao Haiyang Chemical Co. Ltd, China) and TLC measurements were performed on silica gel GF254 plates (Qingdao Haiyang Chemical Co. Ltd, P.R. China). Preparation of multiple-acidic ionic liquids. according to our previous methods

All the ionic liquids were synthesized

[18]

. They were analyzed by 1H NMR,

13

C NMR, and MS

spectroscopic methods, and the spectral data agreed with their structures (Fig. 1). General Procedure for Synthesis of α-Amino phosphonates Catalyzed by [SFHEA][HSO4]. In a typical experiment, to a round-bottom flask charged with aldehyde (5 mmol), aniline (5 mmol), diethyl phosphite (5 mmol), and [SFHEA][HSO4] (0.5 mmol) was added under stirring. The mixture was stirred at room temperature. On completion (monitored by TLC), the mixture was extracted with ethyl acetate several times. The combined organic phase was concentrated through vacuum evaporation, and the resulting crude product was purified by recrystallization in 3



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ethanol to give the desired product. The ionic liquid [SFHEA][HSO4] after extraction was dried in vacuo at 60°C for 5 h. The recovered ionic liquid was then reused in subsequent reactions. NMR spectra of all products prepared are provided in supplementary information. Results and discussion To optimize the reaction conditions, the reaction of benzaldehyde (5 mmol), aniline (5 mmol), and diethyl phosphite (5 mmol) was studied in various conditions at room temperature (Table 1). The reaction did not proceed at all in absence of ionic liquid (Table 1, entry 1), which indicated that the catalysts were absolutely necessary for this one-pot three-component reaction. Then we used 2-hydroxyethylammonium formate, which does not contain any acidic group as catalyst, only 25% yield of product was obtained in 2 h( Table 1, entry 2). To our pleasure, the model reaction proceeded smoothly in the presence of the ionic liquids we synthesized, leading to 82−91% yields of product (Table 1, entries 3−6). Among the four ionic liquids tested, [SFHEA][HSO4] was the most effective, and an excellent yield of 91% was obtained. Then we optimized the amount of [SFHEA][HSO4], the reaction was carried out in the presence of 5, 10, 15 and 20 mol % under solvent-free conditions at room temperature (Table 1, entries 6−9). The best catalyst loading was found to be 10 mol %. Then we added some organic solvents and water, no significant change was found (Table 1, entries 10−13). Consequently, the reaction conditions of 10 mol % of [SFHEA][HSO4] as the catalyst at room temperature without any organic solvent were subjected to further examination. Table 1 Optimization of Reaction Conditions

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Entry

IL (mol%)

Solvent

Time (h)

Yield (%)a

1

Blank

−

2

NRb

2

2-hydroxyethylammoniu

−

2

25

m formate 3

[SFHEA][NO3] (20)

−

2

82

4

[SFHEA][CF3COO] (20)

−

2

83

5

[SFHEA][CH3SO3] (20)

−

2

86

6

[SFHEA][HSO4] (20)

−

2

91

7

[SFHEA][HSO4] (5)

−

2

83

8

[SFHEA][HSO4] (10)

−

2

91

9

[SFHEA][HSO4] (15)

−

2

90

10

[SFHEA][HSO4] (10)

H2 O

2

84

11

[SFHEA][HSO4] (10)

CH3CN

2

85

12

[SFHEA][HSO4] (10)

EtOH

2

91

13

[SFHEA][HSO4] (10)

CHCl3

2

89

a

Isolated yield.

b

NR: no reaction. With the optimal conditions in hand, this condensation reaction with various aldehydes, amines,

and diethyl phosphite in the presence of [SFHEA][HSO4] as the catalyst was explored, and the results are presented in Table 2. It can easily be seen that this one-pot, three-component 5



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condensation completed within 2 h, and the reaction yield was high. For aromatic aldehydes carrying either electron-donating or electron-withdrawing substituents could afford good yields of α-amino phosphonates, and the latter is more reactive. While in the case of anilines, the electron-donating substituents were more reactive. In addition, hetero aromatic aldehydes also show good results (Entries 9, 17, Table 2). Encouraged by these satisfying results, we attempted the reaction with aliphatic aldehydes and ketones. The results indicated the aliphatic aldehydes could react well in the catalytic system (Entries 18, 19, Table 2), while the ketones almost could not react at all even the reaction time was prolonged. Table 2 One-Pot Three-Component Condensation for α-Aminophosphonatesa

Entry

R1

R2

Time

Yield (%)b

Mp/Lit(℃)

(h) 1

C6H5

C6H5

1

91

90-91/89-90[19]

2

2-OCH3C6H4

C6H5

2

81

99-100/98-99[20]

3

3-OCH3C6H4

C6H5

1.5

85

102-103/102-104[21]

4

4-OCH3C6H4

C6H5

1.5

87

102-103/102-103[22]

5

4-OHC6H4

C6H5

1.5

84

-

6

3,4-OCH3C6H3

C6H5

1.5

83

-

7

3-NO2C6H4

C6H5

1

92

96-97/95-97[23]

8

4-NO2C6H4

C6H5

1

93

124-125/125-126[23]

9

2-thienyl

C6H5

2

86

-

6


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a

10

C6H5

3-CH3C6H4

1

91

136-137/134-135[24]

11

C6H5

4-ClC6H4

1.5

88

111-112/113-114[22]

12

C6H5

4-EtOC6H4

1

93

-

13

C6H5

2-CH3C6H4

1.5

86

45-46/43-46[25]

14

C6H5

4-NO2C6H4

1.5

88

146-147/143-144[26]

15

C6H5

4-OCH3C6H4

1.5

94

71-72/70-73[27]

16

C6H5

2-ClC6H4

2

83

84-85/85-86[23]

17

2-furyl

4-OCH3C6H4

2

87

-

18

(CH3)2CH

C6H5

1

85

-

19

CH3CH2

C6H5

1

86

-

5 mmol benzaldehyde, 5 mmol aniline, 5 mmol diethyl phosphite, and 0.5 mmol

[SFHEA][HSO4], r.t. b

Isolated yields. The structure of α-amino phosphonate derivatives in Table 2 was thoroughly characterized with

spectral analysis. Take entry 6 for example, the 1H NMR spectrum showed two triplets at δ 1.31, 1.17 for two methyl protons, two singlets at δ 3.89, 3.87 for two methoxyl protons on benzene ring, one doublet at δ 4.71 for CH. In 13C NMR spectra, peaks in the range of δ 110.7-149.0 correspond to aromatic carbons and the singlets at δ 16.4, 16.3 for two methyl carbon. It’s noticeable that the groups which closed to phosphorus atom showed splitting. So we also characterized the structure by H-H COSY. In the spectral (Fig. 2), A indicates a coupling interaction between the H at 1.2 ppm and the H at 4.0 ppm. This corresponds to the coupling of the CH3 group and the H on CH2. B indicates a coupling interaction between the H at 1.3 ppm and the H at 4.2 ppm. This

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corresponds to the coupling of the CH3 group and the CH2 group. C indicates a coupling interaction between the H at 1.2 ppm and the H at 3.7 ppm. This corresponds to the coupling of the CH3 group and the H on CH2.

Fig. 2 H-H COSY of compound Entry 1 in Table 2. For the purpose of comparison with other methodologies in terms of catalytic efficiency, we carried out the reaction of the 4-nitrobenzaldehyde, aniline and diethyl phosphite. As shown in Table 3, good yields were obtained in the presence of ionic liquids [bmim][BF4] and [bmim][PF6] with a long reaction time(Table 3, entries 1−2). Then, Lewis acid FeCl3 as the catalyst while THF was selected as solvent, and good yield of product was obtained in a short time (Table 3, entry 3). Using Baker’s yeast as biocatalyst, however, the reaction proceeded slowly in 48h, and only

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moderate yield was obtained (Table 3, entry 4). Heterogeneous catalyst, such as Fe/SWCNTs, could give good yields in a short time, while the reaction should be carried on at 50°C (Table 3, entry 5). All of the results demonstrate that the present catalytic system is very efficient for the preparation of α-amino phosphonates (Table 3, entry 6). Table 3 Comparison of the Present Catalytic System with Other Reported Protocols in the Model Reaction between 4-Nitrobenzaldehyde, Aniline and Diethyl phosphite. Entry

Reaction conditions

Yield (%)

Ref.

1

[bmim][BF4](solvent), r.t., 9.5h

80

14

2

[bmim][PF6](solvent), r.t., 12h

71

14

3

FeCl3/THF(10 mol%), r.t., 3h

85

10

4

Baker’s yeast(500mg/mmol), r.t., 48h

67

28

5

Fe/SWCNTs(5 mol%), 50°C, 3h

85

29

6

[SFHEA][HSO4] (10 mol%), r.t., 1h

93

this work

In order to demonstrate the industrial applicability of this methodology, the reaction of benzaldehyde, aniline, and diethyl phosphite was carried out on a larger scale (100 mmol). The reaction was completed in 1 h. A good yield of 91% for the product was achieved. On the same scale, the recyclability of the catalytic system was investigated using the same reaction as the model reaction. Upon completion of the reaction, the product was isolated by several cycles of extraction with ethyl acetate, and the residue ionic liquid was dried to remove water at 60 °C under a vacuum. The combined solvent was evaporated by vacuum distillation to give the crude product, which was recrystallized in ethanol to give the product in high purity. The recovered ionic liquid was reused in subsequent reactions. As shown in Fig. 3, no significant decrease in yields

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was observed even after four runs.

Fig. 3 Recyclability investigation of [SFHEA][HSO4] used as a catalyst for the one-pot three components synthesis of α-amino phosphonates. The high activity of [SFHEA][HSO4] catalyzing synthesis of α-amino phosphonates could be rationalized by a proposed mechanism(Fig. 4). We propose that [SFHEA][HSO4] might play a key role in promoting the reaction of aromatic aldehydes and aromatic amines through hydrogen-bonding interaction. The hydrogen-bonding interaction increased the electrophilicity of the aldehydes, which can facilitate the formation of A. Subsequently, the intermediate B was formed through the interaction of the ionic liquid and A, which tends to eliminate a molecule of water to give the C. The hydrogen-bonding interaction between IL and diethyl phosphite enhanced its the nucleophilicity. On the other hand, the hydrogen-bonding interaction between IL and C, could make C more vulnerable to be attacked by diethyl phosphite. Finally, the target products were obtained in high yield.

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Fig. 4 Proposed mechanism for the synthesis of α-amino phosphonates promoted by [SFHEA][HSO4] To verify this plausible mechanism, we commenced from the following role. The strong hydrogen-bonding interactions can probably make the chemical shift value of the carbonyl carbon atom shift from the original position. Take benzaldehyde as an example, we compared the

13

C

NMR spectrums of benzaldehyde and benzaldehyde-[SFHEA][HSO4] mixture. As we guessed, Table 4 showed that the chemical shift of carbonyl carbon atom in benzaldehyde is 192.19 while it is 192.37 in mixture. The offset of 0.18 indicated the possibility of the mechanism. Table 4 13C NMR Data of Benzaldehyde and Benzaldehyde-[SFHEA][HSO4] Mixture δ Structure

Carbon number benzaldehyde

mixture

C1

192.19

192.37

C2

136.36

136.44

C3

129.55

129.73

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C4

128.88

128.89

C5

134.29

134.45

4. Conclusions In summary, we successfully used multiple-acidic ionic liquids for one-pot three components synthesis of α-amino phosphonates under a neat condition. The procedure offers several advantages including short reaction time, good yields, and easy workup procedures. In view of the good catalytic activities, investigations of their further application for other organic transformations are underway in our laboratory.

Ackonwledgements We are grateful for the financial supports for this research by the National Natural Science Foundation of China (Grant 21106090 and 21272169), Foundation of Low Carbon Fatty Amine Engineering Research Center of Zhejiang Province (2012E10033), and Zhejiang Provincial Natural Science Foundation of China (No. LY12B02004 and LQ13B070002).

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[24] Pudovik, A. N.; Pudovik, M. A. Reaction of phosphites with Schiff bases in the presence of phenol. Zhurnal Obshchei Khimii 1969, 39, 1645. [25] Zahouily, M.; Elmakssoudi, A.; Mezdar, A.; Rayadh, A.; Sebti, S. Natural phosphate and potassium fluoride doped natural phosphate catalyzed simple one-pot synthesis of α-amino phosphonates under solvent-free conditions at room temperature. Catal. Commun. 2007, 8, 225. [26] Ghosh, R.; Maiti, S.; Chakraborty, A.; Maiti, D. K. In(OTf)3 catalyzed simple one-pot synthesis of α-amino phosphonates. J. Mol. Catal. A-Chem 2004, 210, 53. [27] Goulioukina, N. S.; Bondarenko, G. N.; Lyubimov, S. E.; Davankov, V. A.; Gavrilov, K. N.; Beletskaya, I. P. Catalytic hydrogenation of α-iminophosphonates as a method for the synthesis of racemic and optically active α-aminophosphonates. Adv. Synth. Catal. 2008, 350, 482. [28] Bhattacharya, A. K.; Mujahid, M. Efficient Bakers' Yeast-Catalyzed Multicomponent Synthesis of -Aminophosphonates in One Pot. Synth. Commun. 2013, 43, 2583. [29] Sharghi, H.; Ebrahimpourmoghaddam, S.; Doroodmand, M. M. Iron-doped single walled carbon nanotubes as an efficient and reusable heterogeneous catalyst for the synthesis of organophosphorus compounds under solvent-free conditions. Tetrahedron 2013, 69, 4708.

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Synthesis of Î±-Amino Phosphonates under a Neat Condition

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