High Efficiency Catalytic Synthesis of N-Sulfonyltriazole in Aqueous Phase by Copper Sulfate/Substituted Thiourea†

doi:10.7503/cjcu20180540

Abstract

Abstract:

The reaction of a series of sulfonyl-containing azides and terminal alkynes indicated that the combination of copper sulfate/substituted thiourea was more suitable for general copper-catalyzed azide-end alkyne ring addition[Cu(Ⅰ) catalyzed azide-alkyne cycloaddition, CuAAC] reaction. The type of reaction was also possible to efficiently catalyze the synthesis of N-sulfonyl-1,2,3-triazole in the aqueous phase. The type of reaction was not sensitive to water and the yield was up to 99% in the aqueous phase. The reaction mixture was stirred in the air under room temperature(25 ℃). The novel system showed high atom-economy and functional-group tolurance. It provided a simple and efficient synthesis method for the synthesis of a series of N-sulfonyltriazoles.

Key words: Azide, Cu(Ⅰ) catalyzed axide-alhyne cycloaddition(CuAAC) reaction;, Aqueous phase, N-Sulfonyltriazole

CLC Number:

O626.4

TrendMD:

DONG Lirong,WANG Siyu,ZHANG Xiaomei,CHENG Jiajia,YUAN Yaofeng. High Efficiency Catalytic Synthesis of N-Sulfonyltriazole in Aqueous Phase by Copper Sulfate/Substituted Thiourea^†[J]. Chem. J. Chinese Universities, 2019, 40(5): 927.

Figures/Tables 4

References 31

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Compd.	Appearance	Yield(%)^*	MS, m/z[M+H]⁺(calcd.)	Compd.	Appearance	Yield(%)^*	MS, m/z[M+H]⁺(calcd.)
1a^[23]	Slite yellow oil	99	198.21(197.03)	3d^[27]	Whilte solid	52	364.22(362.97)
1b^[24]	Slite yellow oil	93	184.19(183.01)	3e	Whilte solid	68	320.76(319.02)
1c^[25]	Slite yellow oil	79	214.21(213.02)	3f^[28]	Slite yellow solid	83	300.35(299.07)
1d^[25]	Slite yellow oil	89	263.08(260.92)	3g^[19]	Whilte solid	98	336.38(335.07)
1e^[24]	Slite yellow oil	99	218.63(216.97)	3h^[27]	Whilte solid	76	300.35(299.07)
1f^[24]	Colorless oil	81	198.21(197.03)	3i^[29]	Whilte solid	64	234.25(233.04)
1g^[23]	Slite yellow oil	99	234.25(233.03)	4A^[19]	Whilte solid	95	314.38(313.09)
1h^[26]	Slite yellow oil	84	198.21(197.03)	4B^[29]	Whilte solid	92	330.37(329.08)
1i^[24]	Yellow oil	72	122.11(120.99)	4C^[27]	Slite yellowoil	88	378.24(376.98)
L1^[23]	White solide	82	229.31(228.07)	4D^[30]	Whilte solid	91	318.34(317.06)
L2^[23]	Whilte solid	51	274.31(273.06)	4E^[29]	Slite yellow oil	85	280.36(279.10)
L3^[23]	Whilte solid	74	243.09(242.34)	4F^[30]	Whilte solid	95	318.34(317.06)
L4^[23]	Slite whilte solid	86	259.34(258.08)	4G^[19]	Whilte solid	99	306.37(305.03)
3a^[19]	Whilte solid	99	299.35(299.07)	4H^[31]	Slite yellow oil	53	334.79(333.03)
3b^[19]	Whilte solid	80	286.32(285.06)	4I^[30]	Whilte solid	76	330.37(329.37)
3c^[19]	Slite yellow solid	95	316.35(315.07)

Compd.	Appearance	Yield(%)^*	MS, m/z[M+H]⁺(calcd.)	Compd.	Appearance	Yield(%)^*	MS, m/z[M+H]⁺(calcd.)
1a^[23]	Slite yellow oil	99	198.21(197.03)	3d^[27]	Whilte solid	52	364.22(362.97)
1b^[24]	Slite yellow oil	93	184.19(183.01)	3e	Whilte solid	68	320.76(319.02)
1c^[25]	Slite yellow oil	79	214.21(213.02)	3f^[28]	Slite yellow solid	83	300.35(299.07)
1d^[25]	Slite yellow oil	89	263.08(260.92)	3g^[19]	Whilte solid	98	336.38(335.07)
1e^[24]	Slite yellow oil	99	218.63(216.97)	3h^[27]	Whilte solid	76	300.35(299.07)
1f^[24]	Colorless oil	81	198.21(197.03)	3i^[29]	Whilte solid	64	234.25(233.04)
1g^[23]	Slite yellow oil	99	234.25(233.03)	4A^[19]	Whilte solid	95	314.38(313.09)
1h^[26]	Slite yellow oil	84	198.21(197.03)	4B^[29]	Whilte solid	92	330.37(329.08)
1i^[24]	Yellow oil	72	122.11(120.99)	4C^[27]	Slite yellowoil	88	378.24(376.98)
L1^[23]	White solide	82	229.31(228.07)	4D^[30]	Whilte solid	91	318.34(317.06)
L2^[23]	Whilte solid	51	274.31(273.06)	4E^[29]	Slite yellow oil	85	280.36(279.10)
L3^[23]	Whilte solid	74	243.09(242.34)	4F^[30]	Whilte solid	95	318.34(317.06)
L4^[23]	Slite whilte solid	86	259.34(258.08)	4G^[19]	Whilte solid	99	306.37(305.03)
3a^[19]	Whilte solid	99	299.35(299.07)	4H^[31]	Slite yellow oil	53	334.79(333.03)
3b^[19]	Whilte solid	80	286.32(285.06)	4I^[30]	Whilte solid	76	330.37(329.37)
3c^[19]	Slite yellow solid	95	316.35(315.07)

Entry	Catalyst(10%)	Additive	x(Thiourea ligand)(%)^a	Solvent	t/h	Yield(%)^c
1	CuCl₂·2H₂O	L4	10	H₂O	12	Trace
2	CuI	L4	10	H₂O	12	33
3	CuSO₄·5H₂O	L4	10	H₂O	12	88
4	CuSO₄·5H₂O	L(thiourea)	10	H₂O	12	NR^d
5	CuSO₄·5H₂O	L1	10	H₂O	12	96
6	CuSO₄·5H₂O	L2	10	H₂O	12	99
7	CuSO₄·5H₂O	L3	10	H₂O	12	83
8	CuSO₄·5H₂O	L2	5	H₂O	12	99
9	CuSO₄·5H₂O	L2	3	H₂O	12	99
10	CuSO₄·5H₂O	L2	1	H₂O	12	99
11	CuSO₄·5H₂O	L2	1	H₂O	6	99
12	CuSO₄·5H₂O	L2	1	EtOH∶H₂O(1∶1)^b	6	97
13	CuSO₄·5H₂O	L2	1	MeOH∶H₂O(1∶1)^b	6	96
14	CuSO₄·5H₂O	L2	1	MeCN∶H₂O(1∶1)^a	12	Trace
15	CuSO₄·5H₂O	L2	1	DCM∶H₂O(1∶1)^a	12	Trace
16	CuSO₄·5H₂O	L2	1	EtOAc∶H₂O(1∶1)^a	12	53
17	CuSO₄·5H₂O	—		H₂O	24	NR^d
18		L2	1	H₂O	24	NR^d

Entry	Catalyst(10%)	Additive	x(Thiourea ligand)(%)^a	Solvent	t/h	Yield(%)^c
1	CuCl₂·2H₂O	L4	10	H₂O	12	Trace
2	CuI	L4	10	H₂O	12	33
3	CuSO₄·5H₂O	L4	10	H₂O	12	88
4	CuSO₄·5H₂O	L(thiourea)	10	H₂O	12	NR^d
5	CuSO₄·5H₂O	L1	10	H₂O	12	96
6	CuSO₄·5H₂O	L2	10	H₂O	12	99
7	CuSO₄·5H₂O	L3	10	H₂O	12	83
8	CuSO₄·5H₂O	L2	5	H₂O	12	99
9	CuSO₄·5H₂O	L2	3	H₂O	12	99
10	CuSO₄·5H₂O	L2	1	H₂O	12	99
11	CuSO₄·5H₂O	L2	1	H₂O	6	99
12	CuSO₄·5H₂O	L2	1	EtOH∶H₂O(1∶1)^b	6	97
13	CuSO₄·5H₂O	L2	1	MeOH∶H₂O(1∶1)^b	6	96
14	CuSO₄·5H₂O	L2	1	MeCN∶H₂O(1∶1)^a	12	Trace
15	CuSO₄·5H₂O	L2	1	DCM∶H₂O(1∶1)^a	12	Trace
16	CuSO₄·5H₂O	L2	1	EtOAc∶H₂O(1∶1)^a	12	53
17	CuSO₄·5H₂O	—		H₂O	24	NR^d
18		L2	1	H₂O	24	NR^d