New Method for Synthesis of Amide Podand Extractants†

doi:10.7503/cjcu20130635

Abstract

Abstract:

Amide podands are a class of very promising extractants for the treatment of high level liquid wastes from nuclear industry. With the rapid development of the spent fuel reprocessing, the current synthesis methods of amide podands have hardly kept pace with the demands of surging. Therefore, it is very essential to explore a new efficient synthesis way. In this work, three amide podand extractants, N,N,N',N'-tetraalkyl-3-oxa-pentane-1,5-diamide, where the alkyl represents butyl, isobutyl and octyl, were synthesized via a mixed anhydrides method. The synthetic route includes the following three-step reaction. Diglycolic anhydride was firstly prepared through the dehydration of diglycolic acid and then reacted with the dialkyl amine to produce mono-substituted oxa-pentaneamide using pyridine as a catalyst. Finally, in the presence of isobutyl chloroformate and 4-methylmorpholine, the amide podand extractant was obtained via the reaction of mono-substituted oxa-pentaneamide with the corresponding secondary amine. Effects of carboxyl activation time and reaction temperature on the synthesis were investigated. The obtained target compounds were characterized by ¹H NMR and MS. The yields of N,N,N',N'-tetrabutyl-3-oxa-pentane-1,5-diamide, N,N,N',N'-tetraisobutyl-3-oxa-pentane-1,5-diamide and N,N,N',N'-tetraoctyl-3-oxa-pentane-1,5-diamide, were 84%, 80% and 57%, respectively. From the above, the mixed anhydrides method may be used in enlarging scale of synthesis of amide podand extractants.

Key words: Mixed anhydrides method, Mono-substituted oxa-pentaneamide, Isobutyl chloroformate, Amide podand

CLC Number:

O622.5

TrendMD:

WU Yuxuan, DING Songdong, LIU Ning, HUANG Song, HUANG Huang, SU Dongping. New Method for Synthesis of Amide Podand Extractants^†[J]. Chem. J. Chinese Universities, 2014, 35(2): 257.

Figures/Tables 5

References 29

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Compd.	Appearance	m.p./℃	Yield(%)	Compd.	Appearance	Yield(%)
3a	White solid	54—57(54^[28])	82	4a	Yellow oily liquid	84
3b	White solid	82—83	80	4b	Yellow oily liquid	80
3c	White solid	44—48(45—46^[29])	72	4c	Yellow oily liquid	57

Compd.	Appearance	m.p./℃	Yield(%)	Compd.	Appearance	Yield(%)
3a	White solid	54—57(54^[28])	82	4a	Yellow oily liquid	84
3b	White solid	82—83	80	4b	Yellow oily liquid	80
3c	White solid	44—48(45—46^[29])	72	4c	Yellow oily liquid	57

Compd.	¹H NMR(400 MHz, CDCl₃), δ	MS, m/z
3a	4.38(s, 2H, OCH₂), 4.20(s, 2H, OCH₂), 3.38—3.34(m, 2H, CH₂), 3.11—3.07(m, 2H, CH₂), 1.55—1.51(m, 4H, CH₂), 1.32(dp, J=14.2, 7.3 Hz, 4H, CH₂), 0.98—0.91(m, 6H, CH₃)
3b	4.42(s, 2H, OCH₂), 4.20(s, 2H, OCH₂), 3.26(d, J=7.6 Hz, 2H, CH₂), 2.96—2.94(d, J=7.6 Hz, 2H, CH₂), 2.08—2.01(m, 1H, CH), 1.98—1.91 (m, 1H, CH), 0.91(dd, J=17.5, 6.6 Hz, 12H, CH₃)
3c	4.38(s, 2H, OCH₂), 4.21(s, 2H, OCH₂), 3.37—3.33(m, 2H, CH₂), 3.09—3.06(m,2H, CH₂), 1.54(s, 4H, CH₂), 1.28(s, 20H, CH₂), 0.89—0.87(m, 6H, CH₃)
4a	4.31(s, 4H, OCH₂), 3.32—3.17(2t, 8H, CH₂), 1.55—1.25(2m, 16H, CH₂), 0.92(dt, J=7.3, 4.3 Hz, 12H, CH₃)	357.3([M+1]⁺), 376.2([M+23]⁺)
4b	4.35(s, 4H, OCH₂), 3.19(d, J=7.5 Hz, 4H, NCH₂), 3.03(d, J=7.6 Hz, 4H, NCH₂), 1.99(dt, J=20.6, 6.8 Hz, 4H, CH), 1.90(dt, J=20.5, 6.8 Hz, 4H, CH), 0.87(t, J=6.7 Hz, 24H, CH₃)	357.4([M+1]⁺), 379.4([M+23]⁺)
4c	4.32(s, 4H, OCH₂), 3.31—3.15(2t, 8H, NCH₂), 1.52(s, 8H, CH₂), 1.27(s, 40H, CH₂), 0.87(dd, J=7.0, 3.3 Hz, 12H, CH₃)	600.6([M+H₃O]⁺)

Compd.	¹H NMR(400 MHz, CDCl₃), δ	MS, m/z
3a	4.38(s, 2H, OCH₂), 4.20(s, 2H, OCH₂), 3.38—3.34(m, 2H, CH₂), 3.11—3.07(m, 2H, CH₂), 1.55—1.51(m, 4H, CH₂), 1.32(dp, J=14.2, 7.3 Hz, 4H, CH₂), 0.98—0.91(m, 6H, CH₃)
3b	4.42(s, 2H, OCH₂), 4.20(s, 2H, OCH₂), 3.26(d, J=7.6 Hz, 2H, CH₂), 2.96—2.94(d, J=7.6 Hz, 2H, CH₂), 2.08—2.01(m, 1H, CH), 1.98—1.91 (m, 1H, CH), 0.91(dd, J=17.5, 6.6 Hz, 12H, CH₃)
3c	4.38(s, 2H, OCH₂), 4.21(s, 2H, OCH₂), 3.37—3.33(m, 2H, CH₂), 3.09—3.06(m,2H, CH₂), 1.54(s, 4H, CH₂), 1.28(s, 20H, CH₂), 0.89—0.87(m, 6H, CH₃)
4a	4.31(s, 4H, OCH₂), 3.32—3.17(2t, 8H, CH₂), 1.55—1.25(2m, 16H, CH₂), 0.92(dt, J=7.3, 4.3 Hz, 12H, CH₃)	357.3([M+1]⁺), 376.2([M+23]⁺)
4b	4.35(s, 4H, OCH₂), 3.19(d, J=7.5 Hz, 4H, NCH₂), 3.03(d, J=7.6 Hz, 4H, NCH₂), 1.99(dt, J=20.6, 6.8 Hz, 4H, CH), 1.90(dt, J=20.5, 6.8 Hz, 4H, CH), 0.87(t, J=6.7 Hz, 24H, CH₃)	357.4([M+1]⁺), 379.4([M+23]⁺)
4c	4.32(s, 4H, OCH₂), 3.31—3.15(2t, 8H, NCH₂), 1.52(s, 8H, CH₂), 1.27(s, 40H, CH₂), 0.87(dd, J=7.0, 3.3 Hz, 12H, CH₃)	600.6([M+H₃O]⁺)