Syntheses of naphthyl-based quaternary ammonium surfactants and their catalytic properties in chloromethylation of naphthalene

Journal Pre-proof Syntheses of naphthyl-based quaternary ammonium surfactants and their catalytic properties in chloromethylation of naphthalene

Feng Qian, Hong-Yong Zhou, Jia-Xi Wang PII:

S0167-7322(19)36511-0

DOI:

https://doi.org/10.1016/j.molliq.2020.112557

Reference:

MOLLIQ 112557

To appear in:

Journal of Molecular Liquids

Received date:

27 November 2019

Revised date:

10 January 2020

Accepted date:

22 January 2020

Please cite this article as: F. Qian, H.-Y. Zhou and J.-X. Wang, Syntheses of naphthylbased quaternary ammonium surfactants and their catalytic properties in chloromethylation of naphthalene, Journal of Molecular Liquids(2020), https://doi.org/ 10.1016/j.molliq.2020.112557

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© 2020 Published by Elsevier.

Journal Pre-proof

Syntheses of naphthyl-based quaternary ammonium surfactants and their catalytic properties in chloromethylation of naphthalene Feng Qian1, Hong-Yong Zhou1, Jia-Xi Wang *,1,2,3 School of Chemical Engineering and Technology, Hebei University of Technology,

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1

Hebei Provincial Key Lab of Green Chemical Technology and High Efficient

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2

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Tianjin 300130, China

National-Local Joint Engineering Laboratory for Energy Conservation of Chemical

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3

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Energy Saving, Hebei University of Technology, Tianjin 300130, China

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Tianjin 300130, China

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Process Integration and Resources Utilization, Hebei University of Technology,

Abstract: Two naphthyl-based quaternary ammonium surfactants Naph-GS and Naph-MS were synthesized by reaction of bis(chloromethyl)naphthalene and chloromethyl naphthalene with N, N-dimethyl long-chain alkyl tertiary amine. The purified products were characterized by FT-IR and ESI-HRMS. The critical micelle concentration and surface tension（γCMC）at the critical micelle concentration (CMC) of Naph-MS and Naph-GS are 3.70 mmol/L, 27.90 mN/m; 0.89 mmol/L and 31.60 mN/m, respectively. The CMC of Naph-MS is about four times higher than that of Naph-GS. The sizes of most micelles of Naph-MS and Naph-GS aqueous solution at 1.1 CMC are both less than 1 nm. While at the concentration of 11 CMC, most of the Naph-MS, the Naph-GS micelles aggregate forming particles with an average size of 1

Journal Pre-proof 1.2 nm and 10 nm, respectively. The Naph-MS and Naph-GS were used to promote the the chloromethylation reaction of naphthalene. The conversion of naphthalene was 77% when the reaction was catalyzed by Naph-MS (2.5 mol % of naphthalene at 48 mmol/L) at mole ratio of naphthalene / paraformaldehyde /NaCl/H2SO4 being 1.0 : 1.0 : 1.7 : 6.3 at 70℃for 12h. At the same condition, the conversion of naphthalene was 82% when the reaction was promoted by Naph-GS (0.53 mol % of naphthalene at 10 mmol/L). When the mole ratio of naphthalene / paraformaldehyde was increased to 1.25, the conversion of naphthalene increased to 90%, and the positioning selectivity

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(1-chloromethyl to 2-chloromethyl) is 94.8%. The gemini surfactant Naph-GS has

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better catalytic performance than conventional Naph-MS in the chloromethylation of naphthalene. The inorganic aqueous solution can be recycled by simple separation,

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and the conversion of naphthalene can still remain at 85% after 5 cycles.

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Keywords: naphthyl-based surfactant； quaternary ammonium salt；gemini ；surface

1. Introduction

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activity；micellar catalysis；chloromethylation

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Chloromethylation of aromatic compound is a very important reaction which has been widely used in the synthesis of fine chemicals such as pesticides and dyes[1].

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The most commonly employed procedures for chloromethylation aromatic compounds are using chloromethyl methyl ether, bis-chloromethyl ether or other reagents (which can provide formaldehyde, acid and Cl-) as chloromethylation reagents, and using Lewis acid as the catalyst[2]. However, Lewis acid could also catalyze further Friedel-Crafts alkylation of chloromethylated aromatic compounds, which resulted in low selectivity for single chloromethylation. Moreover, the strong carcinogenicity of chloromethyl methyl ether makes those procedures environmental unfriendly.

Therefore,

developing

an

environmentally

friendly

aromatic

chloromethylation process has an important theoretical significance and great application prospect. As a reaction medium, micelles can improve the mass transfer rate between the oil-water phases in a heterogeneous system. The fast mass transfer of the reactants 2

Journal Pre-proof and products between the micellar, organic phase and water phase dramatically increase the reaction rate and selectivity. Micellar catalysis has been widely used in organic synthesis, such as Friedel-Crafts reaction[3,4], Diels-Alder reaction[5–7], oxidation of alcohol in aqueous medium[8–12], and many more reactions[13–15]. Especially, due to gemini surfactants possess several advantages such as lower CMC[16] and better solubilization[17], the application of gemini surfactants in micellar catalysis is receiving more and more attention in recent years[18–22]. Liu et al[23–26]. have reported the chloromethylation of aromatic compounds catalyzed by

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single-chain cationic quaternary ammonium salts, anionic and nonionic surfactant.

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The results showed that the quaternary ammonium salt surfactant has higher catalytic activity among the three kind of surfactants. Hu et al[27]. reported an efficient

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procedure for chloromethylation of aromatics catalyzed by PEG1000-dicationic ionic

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liquids in aqueous media and achieved good results. However, in order to get higher

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yield, it is still necessary to input dry the hydrogen chloride gas continuously during the procedure, which is cumbersome to operate. Our research group[28] has reported

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the application of a thermo-responsive polystyrene with PEG and quaternary ammonium salt side chain in the chloromethylation of naphthalene, and achieved

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excellent catalytic performance.

In this paper, in order to explore the high-efficiency micelle catalyst used in chloromethylation of aromatics, based on the principle of similar miscibility of aromatic compounds, naphthyl-based mono surfactant (Naph-MS) and naphthyl-based gemini surfactant (Naph-GS) were synthesized by the reaction of chloromethyl naphthalene with N, N-dimethyl long-chain alkyl tertiary amine. The surface properties and catalytic performance of these two surfactants were also investigated.

2.Experiment section 2.1 Materials Chloromethyl naphthalene, >97%, laboratory synthesis; N, N-dimethyl long-chain

alkyl

tertiary

amine,

>97%

(N,N-Dimethyldodecylamine

80%,

N,N-Dimethyltetradecylamine 17%) was obtained from Shanghai Xian Ding 3

Journal Pre-proof Biological Technology Co.(Shanghai, China). Other reagents, analytical grade, were obtained from Fuchen Tianjin Chemical Co. (Tianjin, China).

2.2 Synthesis of Naphthyl-based quaternary ammonium salt Naph-GS：11.20 g (51.0 mmol) N, N-dimethyl long-chain alkyl tertiary amine and 5.65 g (25.0 mmol) bis(chloromethyl)naphthalene was added to a 250 mL 3-necked flask with 75 mL 1,4-dioxane. The mixture was stirred at 70℃ for 10h. After cooling to room temperature, the brownish yellow solid was separated by vacuum filtration.

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Then, the brownish yellow solid was recrystallized by 1,4-dioxane to remove

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unreacted raw materials, and dried under vacuum to get 13.82 g light yellow powdery

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solid (Naph-GS), yield 85%.

Naph-MS：11.20 g (51.0 mmol) N, N-dimethyl long-chain alkyl tertiary amine and

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8.80 g (50.0 mmol) chloromethyl naphthalene was added to a 250 mL 3-necked flask

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with 75 mL 1,4-dioxane. The mixture was stirred at 70℃ for 10h. After cooling to room temperature, the solvent was removed under reduced pressure and give light

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yellow blocky solid. These light yellow blocky solid was washed by cyclohexane

yield 87%.

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(3×10 mL), and dried under vacuum to get 8.50 g light yellow waxy solid (Naph-MS),

2.3 Structure characterization The infrared (IR) spectra of Naph-MS and Naph-GS were measured on a Bruker TENSOR 27 spectrometer as KBr pallets. The molecular weights of Naph-MS and Naph-GS were examined by Bruker Compact Q-TOF system (HRMS-ESI)

2.4 Critical micelle concentration (CMC) and particle size measurement At (25±1)℃，the γ-lgC curve of Naph-GS and Naph-MS were measured by using a ring-pull liquid film method on BZY-2 type automatic surface tension meter. The critical micelle concentration (CMC) and the surface tension γCMC at the critical micelle concentration were obtained from the inflection point of the curve. The mean micelles sizes of Naph-GS and Naph-MS solution were measured using a Malvern 4

Journal Pre-proof Instrument Zetasizer Nano ZS90.

2.5 Typical procedures for the chloromethylation of naphthalene 2.5.1 Paraformaldehyde and conc. HCl used as chloromethylation reagent. A mixture of naphthalene (2.18 g, 17 mmol), paraformaldehyde (0.64 g, 21.33 mmol), conc. HCl (18.5 mL), quaternary ammonium salt solution (1 mL，contains

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0.096 g Naph-GS) and cyclohexane (4 mL) were added in a 100 mL round flask equipped with reflux condenser and oil-bath. The solution was stirred at 70℃for 12h.

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After the reaction was completed, the reaction mixture was cooled to room

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temperature, the organic phase was separated and the aqueous phase was extracted by 10 mL of cyclohexane. The combined organic phase was neutralized with saturated

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NaHCO3 aqueous solution, and washed by saturated NaCl aqueous solution until

to give the crude products.

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neutral, then dried over anhydrous Na2SO4. The solvent was removed under vacuum

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2.5.2 Paraformaldehyde, sulfuric acid and sodium chloride used as

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chloromethylation reagent as chloromethylation reagent. A mixture of saturated NaCl aqueous solution (5 mL), quaternary ammonium salt solution (1 mL, contains 0.06 g Naph-GS or 0.17 g Naph-MS) and cyclohexane (4 mL) were added in a 100 mL 3-necked flask equipped with reflux condenser. Under stirring in an ice water bath, 8 mL sulfuric acid (13.8 mol/L) was added dropwise to the flask. After the addition was completed, naphthalene (2.18 g,17 mmol) and paraformaldehyde (0.64 g, 21.33 mmol) were added to the reaction mixture, then the flask was transferred to the oil bath, stirred at 70℃for 12h. After the reaction was completed, the post treatment was the same as above.

2.5.3 Recycle of the inorganic phase After the reaction, fresh naphthalene (2.18 g,17 mmol), paraformaldehyde (0.64 g, 21.33 mmol), cyclohexane (4 mL), 2mL sulfuric acid and NaCl (1.8 g,30 mmol) 5

Journal Pre-proof were then added to the residual aqueous phase, which was filtered and extracted by 10 mL of cyclohexane. The solution was stirred at 70℃for 12h. After the reaction was completed, the post treatment was the same as above. The conversion of naphthalene was determined by GC analysis using tetrahydronaphthalene as the internal standard substance. 1H NMR spectra of these products were recorded on a 400-MHz Bruker NMR spectrometer in CDCl3. δ：8.21– 7.45 (m，7H)，5.12（s，α- chloromethyl），4.82（s，β- chloromethyl）。

Synthesis

and

structural

characterization

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3.1

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3.Results and discussion

surfactants and

Naph-MS

were

synthesized

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Naph-GS

of naphthyl-based

by

the

reaction

of

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bis(chloromethyl)naphthalene and chloromethyl naphthalene with N, N-dimethyl

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long-chain alkyl tertiary amine, respectively. The synthetic route is shown in Figure 1.

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Fig.1. Synthesis procedure of Naph-GS and Naph-MS

FT-IR analysis was carried out to verify the structure of Naph-GS and Naph-MS (Fig.2). The peaks at 3012cm-1 and 850cm-1 are assigned to C-H stretching vibration and out-of-plane bending vibration of naphthalene ring, respectively, and the peaks at 2925 cm-1, 2853 cm–1 are attributed to C-H stretching vibration of methyl and methylene. The characteristic peak of (CH2)n （n>4 ） appears at 722cm-1. After quaternization, the C-Cl stretching vibration peak of chloromethyl naphthalene at 715cm-1 disappeared, and the absorption band at 1040 cm−1 and 844 cm-1 corresponding to the C–N stretching and out-of-plane bending vibration of tertiary amine red shift to 986 cm-1、805 cm-1, which confirmed that the occurrence of quaternization. The vibration peak of O-H at 3415cm-1 is assigned to the O-H stretching frequency of water absorbed by quaternary ammonium salt. 6

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Fig.2. Infrared spectra of raw materials and products (Naph-GS, Naph-MS)

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The mass spectra of Naph-GS and Naph-MS were shown in Figures 3a and 3b. Under the positive ion mode, the peaks at 354.3188 and 382.3499 were linked to

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dodecyl and tetradecyl single-chain quaternary ammonium salts (C25H40N+ m/e 354.3155, C27H44N+ m/e 382.3468), respectively. The peaks at 290.2841,304.2996

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and 318.3151 were linked to dodecyl, dodeca-tetradecyl and tetradecyl double-chain quaternary ammonium salts (C40H72N22+ m/e 290.2942, C42H76N22+ m/e 304.2999,

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C44H80N22+ m/e 318.3155), respectively.

Fig.3. The mass spectra of Naph-GS and Naph-MS 7

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3.2 Surface tension and micellization Fig.4 exhibits the lgC vs surface tension (γ) of Naph-GS and Naph-MS. As we can see, the CMC value of Naph-GS and Naph-MS are 0.56 g/L (0.89 mmol/L) and 1.47 g/L (3.70 mmol/L), respectively. The CMC of the Naph-GS is lower than that of Naph-MS, which is due to the gemini Naph-GS forming micelles easier than single-chain Naph-MS. And the equilibrium surface tension (γCMC) of Naph-GS and Naph-MS are 31.6 mN/m and 27.9 mN/m, respectively. The higher γCMC of Naph-GS

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results the higher stability of Naph-GS micelles[29].

Fig.4 Variation in the surface tension with the surfactant concentration at 25 ± 1 °C

In view to further investigate the micelles formed in the Naph-GS and Naph-MS solutions, the size distribution of Naph-GS and Naph-MS at different concentration were determined by dynamic light scattering (Fig.5 and 6). As is seen from Fig.5, the size of most micelles of Naph-MS aqueous solution at 1.1 CMC is less than 1 nm, and a certain number of micelles aggregates forming particles with an average size of 5 and 200 nm. While, the concentration of Naph-MS at 11CMC, most of the micelles aggregate forming particles with an average size of 1.2 nm, and some of the micelle particles further aggregate to form particles with an average size of 200 nm with wider distribution. In contrast, the size of most micelles of Naph-GS aqueous solution at 1.1 CMC is still less than 1 nm, and a certain number of micelles aggregates 8

Journal Pre-proof forming particles with an average size of 200 nm with wider distribution. At the concentration of Naph-GS at 11CMC, small micelles agglomerate to form two kind of micelles with an average size of 10 nm and 400 nm with wider distribution. Compared with the Naph-MS, Naph-GS aqueous solution can form larger micelles at the same concentration. Large micelles can solubilize more reactants, which is more

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na

lP

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beneficial to the better performance of micelle catalysis.

Fig.5. Size distribution of Naph-MS aqueous solution at (a) 4.0 mmol/L, (b) 40 mmol/L

9

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Fig.6. Size distribution of Naph-GS aqueous solution at (a) 1.0 mmol/L, (b) 10 mmol/L

3.3 Catalytic performance of Naph-GS and Naph-MS The chloromethylation of aromatics requires the protonation of formaldehyde in acid medium to form alkylation reagent and chloride anion. When a hydrochloric acid-paraformaldehyde system (hydrogen ion concentration is 10.9 mol/L) was used as the chloromethylation reagent in chloromethylation of naphthalene catalyzed by Naph-GS (0.53 mol % of naphthalene) at 70 °C for 12h, the conversion of naphthalene was 62%. However, under the same reaction conditions with same molar H+,

the

chloromethylation

reagent

of

H2SO4-NaCl-paraformaldehyde

(H+

concentration is 15.8 mol/L) resulted higher conversion of naphthalene (90%). In the 10

Journal Pre-proof H2SO4-NaCl- formaldehyde chloromethylation system, the higher salt concentration (salt effect) makes the phase separation of the reaction liquid easily. After separation of NaHSO4, the rest H2SO4 and quaternary ammonium salt aqueous solution can be recycled (discuss later). So, compared the hydrochloric acid-paraformaldehyde system, the

amount

of

wastewater

chloromethylation

reactions

is

also

were

reduced. carried

Therefore, out

in

the

the

subsequent system

of

H2SO4-NaCl-paraformaldehyde. The catalytic performance of Naph-MS and Naph-GS for the chloromethylation

salt,

Naph-MS

and

Naph-GS

can

obviously

catalyze

the

ro

ammonium

of

of naphthalene is shown in Fig.7. Compared with the reaction with no quaternary

chloromethylation of naphthalene. The conversion of naphthalene increases with the

-p

prolongation of the reaction time, then remains almost unchanged after 6h. As shown

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in Fig.7, the amount of Naph-MS has little effect on the conversion of naphthalene.

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However, under the same reaction conditions promoted by Naph-GS (0.53 mol % of naphthalene at 10 mmol/L), the conversion of naphthalene can reach 82%. The

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than that of Naph-MS.

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catalytic effect of Naph-GS on chloromethylation of naphthalene is obvious better

Fig.7. Kinetic curves of chloromethylation of naphthalene (Reaction conditions: 17 mmol naphthalene, 17 mmol paraformaldehyde, 70°C) 11

Journal Pre-proof The effect of reaction temperature on the conversion of naphthalene in Naph-GS catalyzed naphthalene chloromethylation is shown in Fig. 8. As the reaction temperature increased from 30℃ to 80℃, the conversion of naphthalene and the content of β - chloromethyl naphthalene increased from 26% , 2.8% to 86% and 6.4%, respectively. The

increase

of

reaction

temperature

is

beneficial

to

the

depolymerization of paraformaldehyde and the mass transfer of reactants between micelle and water phase. Since the α-position electrophilic substitution on the naphthalene ring is a kinetic reaction, the β-site electrophilic substitution reaction is a

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thermodynamic reaction, the content of β-position chloromethylation increased with

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the increase of temperature. Therefore, the position selectivity of the reaction is

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decreased with the increase of temperature.

Fig.8. Effect of reaction temperature on the chloromethylation

(Reaction conditions: 17 mmol naphthalene, 17 mmol paraformaldehyde)

Based on the consideration of the conversion of naphthalene and the selectivity of α-chloromethyl naphthalene, the reaction temperature was set at 70℃for further reaction. Next, the influence of molar ratio of paraformaldehyde to naphthalene and amounts of Naph-GS on the conversion were explored (Fig. 9). The conversion of naphthalene increases from 76% to 82% with the concentration of Naph-GS varied from 5 mmol/L to 10 mmol/L, then remains almost unchanged with further increase 12

Journal Pre-proof the concentration of Naph-GS. As the molar ratio of paraformaldehyde to naphthalene increased from 1.0 to 1.25, the conversion of naphthalene increased from 82% to 90%. However, when the molar ratio of paraformaldehyde to naphthalene increased further to 1.35, the conversion of naphthalene only increased over 1%. Moreover, excess amount of paraformaldehyde can result in the formation of poly chloromethylation, which decreases the selectivity of the reaction, and makes the subsequent processing more difficult. Considering the above factors, the optimized condition for chloromethylation pf naphthalene are as following: molar ratio of paraformaldehyde

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na

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to naphthalene being 1.25.

Fig.9. Effect of molar ratio and concentration of Naph-GS on the conversion (Reaction conditions: 17 mmol naphthalene, 17 mmol paraformaldehyde, 12h)

After the chloromethylation reaction, the inorganic phase contains a certain amount of H2SO4, quaternary ammonium salt and the inorganic salts. In order to reduce the pollution of waste water to the environment, the inorganic phase was filtered to remove solid NaHSO4.The liquid phase will mix with some fresh H2SO4 and NaCl, and recycled in next chloromethylation of naphthalene. The catalytic results are shown in Fig.10. After five cycles, the conversion of naphthalene could still reach 85%. 13

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Fig.10 Recycling of recovered inorganic phase

4 Conclusion

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Naphthyl based quaternary ammonium surfactants Naph-MS and Naph-GS were

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successfully synthesized by reaction of chloromethyl naphthalene and N, N-dimethyl long-chain alkyl tertiary amine. The critical micelle concentration of Naph-MS and

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Naph-GS is 3.70 mmol/L and 0.89 mmol/L, respectively. Naphthyl based surfactant can effectively catalyze the chloromethylation of naphthalene, and the catalytic

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performance of the gemini surfactant Naph-GS is better than that of Naph-MS. The conversion of naphthalene is 90% when the reaction was promoted by Naph-GS (0.53 mol % of naphthalene) at mole ratio of naphthalene / paraformaldehyde /NaCl/H2SO4 being 1.0 : 1.25 : 1.7 : 6.3 at 70℃ for 12h, and the positioning selectivity is up to 94.8%. The aqueous phase can be recycled for the next catalytic reaction, and the conversion of naphthalene can be maintained at 85% after 5 cycles. This gemini surfactant Naph-GS has a good application prospect in the chloromethylation of aromatic compounds.

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Author Statement Feng Qian ： Methodology, Investigation, Writing -Original Draft, Writing - Review & Editing. Hong-Yong Zhou：Preparing 1H NMR results, helping in structure

of

characterization. Jia-Xi Wang：Conceptualization, Methodology, Validation, Investigation,

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Resources, Writing - Review & Editing, Supervision.

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Declaration of interests

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The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence

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the work reported in this paper.

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Highlights 

Naphthyl-based gemini (Naph-GS) and mono surfactant (Naph-MS) were synthesized.



Naph-GS has lower critical micelle concentration (CMC).



Naph-GS and Naph-MS were used to catalyze the chloromethylation of

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Naph-GS exhibits greater catalytic performance than Naph-MS.

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

of

naphthalene.

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