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Volumn 67, Issue 26, 2002, Pages 9238-9247

Mono-N-methylation of primary amines with alkyl methyl carbonates over Y faujasites. 2. Kinetics and selectivity

Author keywords

[No Author keywords available]

Indexed keywords

NUCLEOPHILICITY; PSEUDO FIRST ORDER RATE CONSTANT;

EID: 0037184829     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo026057g     Document Type: Article
Times cited : (46)

References (51)
  • 1
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    • (a) Gibson, M. S. In The Chemistry of Amino Groups; Patai, S., Ed.; Interscience Publishers: London, 1968.
    • (1968) The Chemistry of Amino Groups
    • Gibson, M.S.1
  • 4
    • 0345891261 scopus 로고    scopus 로고
    • note
    • Reactions must be run in sealed vessels (autoclaves) at temperatures over the boiling point of DMC (90°C).
  • 8
    • 0347782542 scopus 로고    scopus 로고
    • note
    • The coproduct alcohol ROH (Scheme 2) can in principle, be recycled to the preparation of the carbonate itself.
  • 9
    • 0346522094 scopus 로고    scopus 로고
    • note
    • Initial reaction conditions were chosen on the basis of results already reported by our group (see ref 4).
  • 10
    • 0345891260 scopus 로고    scopus 로고
    • note
    • According to Figure 1, this assumption holds on the condition that the W ratio be ≥4. Hence, eq 2 can be applied for the results of Figure 2 (W = 5).
  • 12
    • 0346522095 scopus 로고
    • Andersen, J. R., Boudart, M., Eds.; Springer-Verlag: Berlin, Chapter 3
    • (b) Carberry, J. J. In Catalysis: Science and Technology; Andersen, J. R., Boudart, M., Eds.; Springer-Verlag: Berlin, 1987; Vol. 8, Chapter 3.
    • (1987) Catalysis: Science and Technology , vol.8
    • Carberry, J.J.1
  • 13
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    • Rabo, J. A., Ed.; ACS Monograph 171; American Chemical Society: Washington, DC; Chapter 7
    • (c) Eberly, P. E. In Zeolite Chemistry and Catalysis; Rabo, J. A., Ed.; ACS Monograph 171; American Chemical Society: Washington, DC, 1976; Chapter 7.
    • (1976) Zeolite Chemistry and Catalysis
    • Eberly, P.E.1
  • 15
    • 0030288864 scopus 로고    scopus 로고
    • As reported by Simpson et al., the most appropriate analysis of this effect for zeolites is the approach of Weisz - Prater. This model, however, was not applicable for reaction 1 because the diffusional coefficients (D) of the reactants were not available. (a) Simpson, M. F.; Wei, J.; Sundaresan, S. Ind. Eng. Chem. Res. 1996, 35, 3861. (b) Weisz, P. B.; Prater, C. D. Adv. Catal. 1954, 6, 143.
    • (1996) Ind. Eng. Chem. Res. , vol.35 , pp. 3861
    • Simpson, M.F.1    Wei, J.2    Sundaresan, S.3
  • 16
    • 72449183180 scopus 로고
    • As reported by Simpson et al., the most appropriate analysis of this effect for zeolites is the approach of Weisz - Prater. This model, however, was not applicable for reaction 1 because the diffusional coefficients (D) of the reactants were not available. (a) Simpson, M. F.; Wei, J.; Sundaresan, S. Ind. Eng. Chem. Res. 1996, 35, 3861. (b) Weisz, P. B.; Prater, C. D. Adv. Catal. 1954, 6, 143.
    • (1954) Adv. Catal. , vol.6 , pp. 143
    • Weisz, P.B.1    Prater, C.D.2
  • 17
    • 0347782541 scopus 로고    scopus 로고
    • note
    • obs values were within a maximum of a 10% deviance from each other.
  • 19
    • 0033722066 scopus 로고    scopus 로고
    • This procedure was also applied to demonstrate the absence of diffusional effects for several reported zeolite-catalyzed reactions, i.e., the N-methylation of melamine catalyzed by Ru mordenites, the trans-alkylation of diethylbenzene/benzene in the presence of H faujasites, and the oligomerization of isobutene with H mordenites. (a) Shinoda, S.; Fujimura, K.; Ohnishi, T.; Yamakawa, T. Appl. Catal., A 2000, 194-195, 375. (b) Tiako Ngandjui, L. M.; Louhibi, D.; Thyrion, F. C. Chem. Eng. Process. 1997, 36, 133. (c) Tiako Ngandjui, L. M., Thyrion, F. C. Chem. Eng. Process. 1992, 31, 1.
    • (2000) Appl. Catal., A , vol.194-195 , pp. 375
    • Shinoda, S.1    Fujimura, K.2    Ohnishi, T.3    Yamakawa, T.4
  • 20
    • 0031123910 scopus 로고    scopus 로고
    • This procedure was also applied to demonstrate the absence of diffusional effects for several reported zeolite-catalyzed reactions, i.e., the N-methylation of melamine catalyzed by Ru mordenites, the trans-alkylation of diethylbenzene/benzene in the presence of H faujasites, and the oligomerization of isobutene with H mordenites. (a) Shinoda, S.; Fujimura, K.; Ohnishi, T.; Yamakawa, T. Appl. Catal., A 2000, 194-195, 375. (b) Tiako Ngandjui, L. M.; Louhibi, D.; Thyrion, F. C. Chem. Eng. Process. 1997, 36, 133. (c) Tiako Ngandjui, L. M., Thyrion, F. C. Chem. Eng. Process. 1992, 31, 1.
    • (1997) Chem. Eng. Process. , vol.36 , pp. 133
    • Tiako Ngandjui, L.M.1    Louhibi, D.2    Thyrion, F.C.3
  • 21
    • 0026853852 scopus 로고
    • This procedure was also applied to demonstrate the absence of diffusional effects for several reported zeolite-catalyzed reactions, i.e., the N-methylation of melamine catalyzed by Ru mordenites, the trans-alkylation of diethylbenzene/benzene in the presence of H faujasites, and the oligomerization of isobutene with H mordenites. (a) Shinoda, S.; Fujimura, K.; Ohnishi, T.; Yamakawa, T. Appl. Catal., A 2000, 194-195, 375. (b) Tiako Ngandjui, L. M.; Louhibi, D.; Thyrion, F. C. Chem. Eng. Process. 1997, 36, 133. (c) Tiako Ngandjui, L. M., Thyrion, F. C. Chem. Eng. Process. 1992, 31, 1.
    • (1992) Chem. Eng. Process. , vol.31 , pp. 1
    • Tiako Ngandjui, L.M.1    Thyrion, F.C.2
  • 25
    • 0347782536 scopus 로고    scopus 로고
    • note
    • Zeolites are known to be hygroscopic solids. Before each reaction, the catalyst was dried with heating overnight at 70°C and under vacuum (10 mm). This treatment was not applied in the case of entry 3 in Table 1. The dried zeolite showed a weight decrease in the range of 5-7% (determined through a gravimetric comparison between three dried and nondried samples).
  • 26
    • 0347152413 scopus 로고    scopus 로고
    • note
    • obs (entries 1-3).
  • 29
    • 0345891257 scopus 로고    scopus 로고
    • note
    • obs values were not determinable.
  • 30
    • 0347782537 scopus 로고    scopus 로고
    • note
    • 3 (see the Experimental Section).
  • 34
    • 0346522086 scopus 로고    scopus 로고
    • Thesis, University of Ca' Foscari, Venezia, Italy
    • Berto, C. Thesis, University of Ca' Foscari, Venezia, Italy, 2001.
    • (2001)
    • Berto, C.1
  • 36
    • 0347152412 scopus 로고    scopus 로고
    • note
    • The carbonate 2a was advantageous for high-temperature methylation reactions (T > 120°C). However, since benzylamine was rapidly methylated also at a lower temperature (90°C), DMC (a commercially available compound) could be used more conveniently at its reflux temperature (90°C) and at atmospheric pressure.
  • 38
    • 0039855249 scopus 로고
    • (b) Su, B.; Barthomeuf, D. Stud. Surf. Sci. Catal. 1995, 94, 598. Actually, ref31b reports that Y faujasites possess only Lewis-type acidity, the Brönsted contribution of OH groups on the surface being negligible.
    • (1995) Stud. Surf. Sci. Catal. , vol.94 , pp. 598
    • Su, B.1    Barthomeuf, D.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.