Synthesis and Group Transfer Reaction of 1-Methyl-2-isopropyl(or propyl)-3-benzenesulfonyl Imidazolidinium Iodide†

doi:10.7503/cjcu20141144

Abstract

Abstract:

In the course of developing synthetic methods based upon mechanisms of biochemical processes, 1-methyl-2-isopropyl-3-benzenesulfonyl imidazolidinium iodide(5a) and 1-methyl-2-propyl-3-benzenesulfonyl imidazolidinium iodide(5b) were prepared as the tetrahydrofolate model compounds at the oxidation level of formate, which reacting with bifunctional nucleophiles o-phenylenediamine and 2-aminophenol. In the synthe-tic process, four carbon fragments were transferred completely and we found a way directly to benzimidazoles, benzoxazoles. The reaction of the model compound 5a with monofunctional nucleophiles(butylamine, aniline, benzylamine, p-methoxyaniline) afforded the products transferred part of four carbon fragments, containing three different groups of N,N,N'-trisubstituted ethylenediamine salt. Sodium borohydride reduction of 5a afforded compound 9. Treatment of compound 5a with NaOH caused hydrolysis and the corresponding carbonyl compound 10 was formed. The nucleophilic addition reaction of compound 5a with some carbanion(nitrome-thane carbanion and malononitrile carbanion) gave compounds 12 and 13, respectively. Compounds 9, 10, and 12 or 13 are three kinds of containing different groups of N,N,N'-trisubstituted ethylenediamine.

Key words: Tetrahydrofolate, Imidazolinium salt, Transfer reaction, Model, Addition action

CLC Number:

O621.3

TrendMD:

WEN Xueshan, HUO Mingzhang, CHEN Jianxin. Synthesis and Group Transfer Reaction of 1-Methyl-2-isopropyl(or propyl)-3-benzenesulfonyl Imidazolidinium Iodide^†[J]. Chem. J. Chinese Universities, 2015, 36(5): 893.

Figures/Tables 9

Fig.1 Structure of THF(1) and three kinds of oxidation levels of THF(2—4)

Fig.2 Structures of THF model compounds 5a and 5b

Table 1 Appearance, yields, IR, melting points and elemental analysis results of compounds 5a, 5b, 8a—8d, 9, 10, 12 and 13

Compd.	Appearance	Yield(%)	m.p./℃	IR(KBr), $ν ˙$ /cm^-1	Elemental analysis(%, calcd.)
Compd.	Appearance	Yield(%)	m.p./℃	IR(KBr), $ν ˙$ /cm^-1	C	H	N
5a	Colourless crystals	89.0	134.0—135.0	1679, 1626, 1452, 1190	39.59(39.60)	4.82(4.86)	7.25(7.11)
5b	Yellowish crystals	87.0	126.0—127.5	1680, 1624, 1452, 1190	39.32(39.60)	4.61(4.86)	6.88(7.11)
8a	Yellowish crystals	76.0	124.0—126.0	3488, 1605, 1312, 1237, 1123	43.51(43.68)	6.23(6.47)	8.82(8.99)
8b	Colourless crystals	91.4	120.0—121.0	3486, 1612, 1322, 1223, 1135	47.83(47.91)	5.42(5.63)	8.21(8.38)
8c	Colourless crystals	55.3	119.0—120.0	3487, 1601, 1323, 1186, 1134	46.90(46.82)	5.25(5.38)	8.45(8.62)
8d	Colourless crystals	49.2	103.0—105.0	3485, 1613, 1512, 1223, 1135	46.55(46.43)	5.61(5.45)	8.28(8.12)
9	Colourless liquids	76.4		3486, 1552, 1456, 1135	57.83(57.75)	8.32(8.20)	10.42(10.36)
10	Colourless crystals	85.4	98.5—100.0	3469, 1669, 1550, 1435	54.64(54.91)	7.16(7.09)	9.74(9.85)
12	Colourless crystals	88.2	102.0—104.0	3489, 1649, 1450, 1335, 1187	51.35(51.36)	6.44(6.46)	12.70(12.83)
13	Colourless crystals	67.6	106.0—107.0	3481, 2241, 1643, 1513, 1326	58.01(57.78)	6.07(6.06)	16.62(16.85)

Table 1 Appearance, yields, IR, melting points and elemental analysis results of compounds 5a, 5b, 8a—8d, 9, 10, 12 and 13

Compd.	Appearance	Yield(%)	m.p./℃	IR(KBr), $ν ˙$ /cm^-1	Elemental analysis(%, calcd.)
Compd.	Appearance	Yield(%)	m.p./℃	IR(KBr), $ν ˙$ /cm^-1	C	H	N
5a	Colourless crystals	89.0	134.0—135.0	1679, 1626, 1452, 1190	39.59(39.60)	4.82(4.86)	7.25(7.11)
5b	Yellowish crystals	87.0	126.0—127.5	1680, 1624, 1452, 1190	39.32(39.60)	4.61(4.86)	6.88(7.11)
8a	Yellowish crystals	76.0	124.0—126.0	3488, 1605, 1312, 1237, 1123	43.51(43.68)	6.23(6.47)	8.82(8.99)
8b	Colourless crystals	91.4	120.0—121.0	3486, 1612, 1322, 1223, 1135	47.83(47.91)	5.42(5.63)	8.21(8.38)
8c	Colourless crystals	55.3	119.0—120.0	3487, 1601, 1323, 1186, 1134	46.90(46.82)	5.25(5.38)	8.45(8.62)
8d	Colourless crystals	49.2	103.0—105.0	3485, 1613, 1512, 1223, 1135	46.55(46.43)	5.61(5.45)	8.28(8.12)
9	Colourless liquids	76.4		3486, 1552, 1456, 1135	57.83(57.75)	8.32(8.20)	10.42(10.36)
10	Colourless crystals	85.4	98.5—100.0	3469, 1669, 1550, 1435	54.64(54.91)	7.16(7.09)	9.74(9.85)
12	Colourless crystals	88.2	102.0—104.0	3489, 1649, 1450, 1335, 1187	51.35(51.36)	6.44(6.46)	12.70(12.83)
13	Colourless crystals	67.6	106.0—107.0	3481, 2241, 1643, 1513, 1326	58.01(57.78)	6.07(6.06)	16.62(16.85)

Table 2 1H NMR and 13C NMR data of compounds 5a, 5b, 8a—8d, 9, 10, 12 and 13

Compd.	¹H NMR(600 MHz)	¹³C NMR(151 MHz)
5a^a	7.73—8.15(m, 5H), 4.57(t, J=10.2 Hz, 2H), 4.46(t, J=10.2 Hz, 2H), 3.65—3.70(m, 1H), 3.47(s, 3H), 1.28(d, J=7.2 Hz, 6H)	172.0, 136.2, 136.0, 130.7, 128.1, 53.0, 48.4, 37.5, 26.3, 17.7
5b^a	7.70—8.13(m, 5H), 4.29, (s, 4H), 3.40(s, 3H), 3.01(t, J=7.8 Hz, 2H), 1.68—1.77(m, 2H), 1.11(t, J=7.8 Hz, 3H)	169.7, 136.0, 135.0, 130.4, 128.6, 52.1, 47.3, 36.6, 28.7, 20.4, 14.4
8a^b	7.92(brs, 1H), 7.63—7.82(m, 5H), 3.62(brs, 2H), 3.44(brs, 2H), 3.34—3.41(m, 3H), 3.21(brs, 1H), 3.01(brs, 3H), 1.56(m, 2H), 1.24—1.35(m, 8H), 0.91(t, J=7.6 Hz, 3H)	170.5, 140.6, 133.2, 129.9, 126.9, 53.5, 44.6, 40.6, 32.4, 31.4, 27.4, 19.6, 18.6, 14.1
8b^b	7.97(brs, 1H), 7.64—7.84(m, 5H), 7.33—7.42(m, 5H), 4.76—4.21(m, 2H), 3.66(brs, 2H), 3.33(s, 3H), 3.10—3.16(m, 2H), 3.01—3.08(m, 2H), 1.26—1.20(m, 6H)	171.2, 140.5, 137.7, 133.3, 129.9, 129.1, 127.9, 127.0, 126.9, 53.6, 47.3, 40.5, 27.7, 18.5, 17.8
8c^b	7.60—7.81(m, 10H), 4.05(s, 1H), 3.26—3.34(m, 4H), 3.10(s, 3H), 2.97(s, 1H), 1.27(s, 1H), 0.96(d, J=6.8 Hz, 6H)	172.4, 140.6, 138.1, 132.2, 128.3, 128.1, 126.5, 124.1, 123.3, 55.1, 32.1, 30.6, 20.8, 19.6
Compd.	¹H NMR(600 MHz)	¹³C NMR(151 MHz)
8d^b	10.20, 7.99(brss, 1H), 7.66—7.84(m, 5H), 7.06—7.26(m, 4H), 3.80(s, 3H), 3.70(brs, 2H), 3.09—3.35(m, 7H), 1.25(brs, 6H)	171.7, 159.3, 140.5, 133.3, 129.9, 129.6, 128.3, 126.9, 115.1, 56.0, 53.2, 40.5, 30.5, 19.4, 18.6
9^a	7.51—7.89(m, 5H), 5.50(s, 1H), 3.02(t, J=6.0 Hz, 2H), 2.46(t, J=6.0 Hz, 2H), 2.10(s, 3H), 1.95(d, J=7.5 Hz, 2H), 1.68—1.72(m, 1H), 0.83(d, J=6.6 Hz, 6H)	139.5, 132.7, 129.1, 126.9, 65.5, 55.9, 41.7, 40.0, 25.8, 20.6
10^a	7.47—7.87(m, 5H), 6.43, 6.08(ss, 1H), 3.44—3.47(m, 2H), 3.00—3.15(m, 2H), 2.98, 2.85(ss, 3H), 2.72—2.74(m, 1H), 1.10—1.11(m, 6H)	178.7, 175.6, 140.1, 140.0, 132.7, 132.5, 129.2, 129.1, 126.9, 126.8, 49.6, 47.5, 41.4, 41.1, 35.9, 33.8, 30.5, 29.9, 19.7, 19.1
12^a	7.47—7.86(m, 5H), 6.07(br s, 1H), 3.46(t, J=6.0 Hz, 2H), 3.11(t, J=6.0 Hz, 2H), 2.99(s, 3H), 2.84(s, 1H), 2.71—2.75(m, 1H), 1.12(d, J=6.6 Hz, 6H)	178.7, 140.1, 132.5, 129.1, 126.9, 49.6, 47.5, 41.5, 35.9, 30.5, 19.7, 19.1
13^a	7.28—7.85(m, 5H), 5.75(t, J=6.0 Hz, 1H), 3.68—3.79(m, 2H), 3.30(s, 3H), 3.21—3.29(m, 1H), 3.11—3.20(m, 2H), 1.39(d, J=7.2 Hz, 6H)	180.6, 139.3, 133.2, 129.5, 126.9, 117.8, 117.5, 54.7, 51.5, 42.8, 40.9, 32.9, 19.5

Table 2 1H NMR and 13C NMR data of compounds 5a, 5b, 8a—8d, 9, 10, 12 and 13

Compd.	¹H NMR(600 MHz)	¹³C NMR(151 MHz)
5a^a	7.73—8.15(m, 5H), 4.57(t, J=10.2 Hz, 2H), 4.46(t, J=10.2 Hz, 2H), 3.65—3.70(m, 1H), 3.47(s, 3H), 1.28(d, J=7.2 Hz, 6H)	172.0, 136.2, 136.0, 130.7, 128.1, 53.0, 48.4, 37.5, 26.3, 17.7
5b^a	7.70—8.13(m, 5H), 4.29, (s, 4H), 3.40(s, 3H), 3.01(t, J=7.8 Hz, 2H), 1.68—1.77(m, 2H), 1.11(t, J=7.8 Hz, 3H)	169.7, 136.0, 135.0, 130.4, 128.6, 52.1, 47.3, 36.6, 28.7, 20.4, 14.4
8a^b	7.92(brs, 1H), 7.63—7.82(m, 5H), 3.62(brs, 2H), 3.44(brs, 2H), 3.34—3.41(m, 3H), 3.21(brs, 1H), 3.01(brs, 3H), 1.56(m, 2H), 1.24—1.35(m, 8H), 0.91(t, J=7.6 Hz, 3H)	170.5, 140.6, 133.2, 129.9, 126.9, 53.5, 44.6, 40.6, 32.4, 31.4, 27.4, 19.6, 18.6, 14.1
8b^b	7.97(brs, 1H), 7.64—7.84(m, 5H), 7.33—7.42(m, 5H), 4.76—4.21(m, 2H), 3.66(brs, 2H), 3.33(s, 3H), 3.10—3.16(m, 2H), 3.01—3.08(m, 2H), 1.26—1.20(m, 6H)	171.2, 140.5, 137.7, 133.3, 129.9, 129.1, 127.9, 127.0, 126.9, 53.6, 47.3, 40.5, 27.7, 18.5, 17.8
8c^b	7.60—7.81(m, 10H), 4.05(s, 1H), 3.26—3.34(m, 4H), 3.10(s, 3H), 2.97(s, 1H), 1.27(s, 1H), 0.96(d, J=6.8 Hz, 6H)	172.4, 140.6, 138.1, 132.2, 128.3, 128.1, 126.5, 124.1, 123.3, 55.1, 32.1, 30.6, 20.8, 19.6
Compd.	¹H NMR(600 MHz)	¹³C NMR(151 MHz)
8d^b	10.20, 7.99(brss, 1H), 7.66—7.84(m, 5H), 7.06—7.26(m, 4H), 3.80(s, 3H), 3.70(brs, 2H), 3.09—3.35(m, 7H), 1.25(brs, 6H)	171.7, 159.3, 140.5, 133.3, 129.9, 129.6, 128.3, 126.9, 115.1, 56.0, 53.2, 40.5, 30.5, 19.4, 18.6
9^a	7.51—7.89(m, 5H), 5.50(s, 1H), 3.02(t, J=6.0 Hz, 2H), 2.46(t, J=6.0 Hz, 2H), 2.10(s, 3H), 1.95(d, J=7.5 Hz, 2H), 1.68—1.72(m, 1H), 0.83(d, J=6.6 Hz, 6H)	139.5, 132.7, 129.1, 126.9, 65.5, 55.9, 41.7, 40.0, 25.8, 20.6
10^a	7.47—7.87(m, 5H), 6.43, 6.08(ss, 1H), 3.44—3.47(m, 2H), 3.00—3.15(m, 2H), 2.98, 2.85(ss, 3H), 2.72—2.74(m, 1H), 1.10—1.11(m, 6H)	178.7, 175.6, 140.1, 140.0, 132.7, 132.5, 129.2, 129.1, 126.9, 126.8, 49.6, 47.5, 41.4, 41.1, 35.9, 33.8, 30.5, 29.9, 19.7, 19.1
12^a	7.47—7.86(m, 5H), 6.07(br s, 1H), 3.46(t, J=6.0 Hz, 2H), 3.11(t, J=6.0 Hz, 2H), 2.99(s, 3H), 2.84(s, 1H), 2.71—2.75(m, 1H), 1.12(d, J=6.6 Hz, 6H)	178.7, 140.1, 132.5, 129.1, 126.9, 49.6, 47.5, 41.5, 35.9, 30.5, 19.7, 19.1
13^a	7.28—7.85(m, 5H), 5.75(t, J=6.0 Hz, 1H), 3.68—3.79(m, 2H), 3.30(s, 3H), 3.21—3.29(m, 1H), 3.11—3.20(m, 2H), 1.39(d, J=7.2 Hz, 6H)	180.6, 139.3, 133.2, 129.5, 126.9, 117.8, 117.5, 54.7, 51.5, 42.8, 40.9, 32.9, 19.5

Fig.3 Structures of compounds 6—8

Fig.4 Structures of compounds 9—13

Fig.5 Molecular structure of compound 8a

Table 3 Crystal data and refinement parameters for compound 8a

Formula	C₁₇H₃₀IN₃O₂S	α/(°)	107.288(6)	θ Range /(°)	3.12—26.37
Formula weight	467.19	β/(°)	90.086(5)	Data/parameters/restraints	8857/533/106
Crystal size/mm³	0.31×0.23×0.11	γ/(°)	102.039(5)	GOF	1.050
Crystal system	Triclinic	V/nm³	2.165(2)	R₁[I>2σ(I)]	0.0630
Space group	P $1 ˉ$	Z	2	Reflections collected(R_int)	16995(0.0451)
a/nm	1.0562(5)	D_c/(g·cm^-3)	1.469	wR₂(all data)	0.2093
b/nm	1.3410(10)	F(000)	968.8
c/nm	1.6411(10)	μ/mm^-1	1.731

Table 3 Crystal data and refinement parameters for compound 8a

Formula	C₁₇H₃₀IN₃O₂S	α/(°)	107.288(6)	θ Range /(°)	3.12—26.37
Formula weight	467.19	β/(°)	90.086(5)	Data/parameters/restraints	8857/533/106
Crystal size/mm³	0.31×0.23×0.11	γ/(°)	102.039(5)	GOF	1.050
Crystal system	Triclinic	V/nm³	2.165(2)	R₁[I>2σ(I)]	0.0630
Space group	P $1 ˉ$	Z	2	Reflections collected(R_int)	16995(0.0451)
a/nm	1.0562(5)	D_c/(g·cm^-3)	1.469	wR₂(all data)	0.2093
b/nm	1.3410(10)	F(000)	968.8
c/nm	1.6411(10)	μ/mm^-1	1.731

Table 4 Selected bond distances(nm) and bond angles(°) for compound 8a

C7—C8	0.1509(8)	C11—C12	0.1533(16)	N2—S1	0.1601(5)	C10—N4	0.1332(8)
C8—N3	0.1462(8)	C12—C13	0.1461(19)	N4—C11	0.1419(10)	C10—C16	0.1524(9)
C9—N3	0.1452(9)	C13—C14	0.1460(19)	O1—S1	0.1419(5)	C16—C17	0.1524(11)
C10—N3	0.1331(8)	C7—N2	0.1472(8)	O2—S1	0.1423(5)	C16—C15	0.1531(10)
N3—C10—N4	118.9(6)	C10—C16—C15	110.6(6)	C10—N4—C11	132.3(7)	N2—C7—C8	110.3(5)
C1—C6—S1	120.6(6)	N4—C10—C16	121.6(6)	C10—N3—C9	118.8(6)	N3—C7—C8	111.7(5)
O1—S1—O2	118.9(3)	C17—C16—C10	112.1(7)	C10—N3—C8	125.6(5)	C7—N2—S1	120.7(5)
C5—C6—S1	119.8(6)	C17—C16—C15	114.8(7)	N3—C10—C16	119.4(6)	C9—N3—C8	115.5(5)

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