NMR Studies on [2 + 3] Cycloaddition of Nitrile Oxides to Polyunsaturated Medium Size Rings

Gucma, Mirosław; Gołębiewski, W. Marek; Michalczyk, Alicja K.

doi:10.5935/0103-5053.20160078

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Articles • J. Braz. Chem. Soc. 27 (11) • Nov 2016 • https://doi.org/10.5935/0103-5053.20160078 copy

NMR Studies on [2 + 3] Cycloaddition of Nitrile Oxides to Polyunsaturated Medium Size Rings

Authorship SCIMAGO INSTITUTIONS RANKINGS

Site selectivity, regioselectivity and stereoselectivity of [2 + 3] cycloaddition of 4-trifluoromethylbenzonitrile oxide to polyunsaturated medium size rings including 1,5,9-cyclododecatriene, 11-membered sesquiterpenes, 1,3-cyclooctadiene and 5-vinyl-2-norbornene were examined. Site selectivity was correlated with electron charges of alkenyl carbon atoms. Structure of the products has been established by an extensive application of 1D and 2D ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy and electrospray ionization mass spectrometry. Some of the obtained products showed moderate fungicidal activities.

Keywords:
[2 + 3] dipolar cycloaddition; sesquiterpenes; site selectivity; 2D NMR; fungicides

H	δ / ppm (J / Hz)
H	14	15	16	17
1	5.09-4.98 (m)	5.53-5.45 (m)	3.37 (ddd, 10.5, 3.0, 1.5)	4.61 (ddd, 10.5, 4.5, 2.0)
2	5.43-5.30 (m)	5.41-5.27 (m)	4.66 (dm, 10.5)	3.46 (dm, 10.5)
3a	2.14-2.07 (m)	2.12-2.05 (m)	1.84-1.79 (m)	1.65-1.60 (m)
3b	2.05-1.99 (m)	2.02-1.96 (m)	1.68-1.62 (m)	1.57-1.51 (m)
4a	2.12-2.08 (m)	2.12-2.08 (m)	2.16-2.12 (m)	2.28-2.21 (m)
4b	2.20-2.14 (m)	2.02-1.96 (m)	2.05-1.98 (m)	2.20-2.18 (m)
5	5.23-5.12 (m)	5.38-5.30 (m)	5.52-5.42 (m)	5.30-5.22 (m)
6	5.43-5.30 (m)	5.23-5.12 (m)	5.40-5.35 (m)	5.52-5.42 (m)
7a	2.06-2.00 (m)	2.22-2.14 (m)	2.37-2.32 (m)	2.27-2.20 (m)
7b	2.02-1.95 (m)	2.11-2.05 (m)	2.15-2.10 (m)	2.16-2.10 (m)
8a	2.24-2.18(m)	1.31-1.22 (m)	2.29-2.20 (m)	2.15-2.10 (m)
8b	1.84-1.76 (m)	1.05 -1.00 (m)	2.15-2.10 (m)	2.12-2.06 (m)
9	4.24 (ddd, 12.5, 10.1, 1.8)	3.41 (dm, 11.2)	5.53-5.42 (m)	5.53-5.43 (m)
10	3.20 (dd, 12.5, 3.2)	4.35-4.30 (m)	5.29-5.22 (m)	5.40-5.34 (m)
11a	1.48-1.36 (m)	2.22-2.14 (m)	2.28-2.21 (m)	2.41-2.30 (m)
11b	1.07-0.98 (m)	1.82-1.77 (m)	2.15-2.10 (m)	2.15-2.10 (m)
12a	2.24-2.18 (m)	2.23-2.16 (m)	1.67-1.62 (m)	1.87-1.83 (m)
12b	2.02-1.95 (m)	2.02-1.95 (m)	1.59-1.53 (m)	1.74-1.68 (m)
2’, 6’	7.80 (d, 8.1)	8.09 (dm, 8.1)	7.83 (d, 8.0)	7.79 (d, 8.0)
3’, 5’	7.67 (dd, 8.1, 2.6)	7.71(dm, 8.1)	7.68 (d, 8.0)	7.68 (d, 8.0)

C	δ / ppm (J / Hz)
C	14	15	16	17
1	130.5	130.9	50.4	85.9
2	131.8	129.3	86.0	49.7
3	32.3	31.6	31.4	28.4
4	31.5	31.7	31.8	30.2
5	129.3	131.5	132.2	129.1
6	130.9	129.0	129.7	130.0
7	27.1	31.2	24.9	32.0
8	29.7	28.6	22.4	24.9
9	87.2	53.9	131.3	130.9
10	56.9	87.4	129.2	129.7
11	30.6	29.7	22.4	24.9
12	31.1	27.0	28.4	32.5
13	159.2	159.4	159.5	159.7
1’	132.5 (q, 2.4)	132.8 (q, 2.4)	132.7 (q, 1.3)	132.8 (q, 1.3)
2’, 6’	127.3	127.1	127.2	127.2
3’, 5’	125.8 (q, 3.8)	125.7 (m)	125.8 (q, 3.7)	125.8 (q, 3.7)
4’	131.2 (q, 32.7)	131.1 (q, 32.6)	131.5 (m)	131.4 (m)
CF3	123.7 (q, 270.9)	124.1 (q, 272.0)	123.7 (q, 270.6)	123.7 (q, 270.6)

H	δ / ppm (J / Hz)
H	24	25	26	27
1a	3.56 (dd, 16.3, 10.5)	3.54 (dd, 16.5, 10.5)	3.53 (dd, 16.5, 10.3)	3.53(dd, 16.3, 10.3)
1b	3.08 (dd, 16.3, 9.4)	3.08 (dd, 16.5, 9.0)	3.07 (dd, 16.5, 8.0)	3.07(dd, 16.3, 8.3)
2	5.01 (ddd, 10.5, 9.4, 4.8)	4.86 (ddd, 10.5, 9.0, 6.5)	4.73-4.65 (m)	4.73-4.65 (m)
3	2.29-2.22 (m)	2.30-2.24 (m)	2.25-2.19 (m)	2.28-2.19 (m)
4a	1.83 (ddd, 12.0, 12.0; 5.5)	1.92(ddd,12.0, 8.0, 4.0)	1.90 (ddd, 10.0, 7.5, 5.4)	1.90 (td, 12.0, 5.0 )
4b	1.18 (ddd,12.0, 5.8, 2.5)	1.40 (dm, 12.0)	0.79 (ddd, 10.0, 5.4, 3.5)	0.79 (dm, 12.0)
5	2.71 (d, 5.0)	2.77 (d, 4.0)	2.82 (bd, 3.5)	2.82 (d, 2.5)
6	4.80 (d, 8.3)	5.16 (d, 8.3)	3.99 (d, 8.3)	3.99 (d, 8.3)
7	4.20 (d, 8.3)	3.69 (d, 8.3)	4.70 (d, 8.3)	4.70 (d, 8.3)
8	2.54 (d, 3.5)	2.56 (bs)	2.70 (d, 5.0)	2.70 (d, 5.0)
9a	1.60 (dm, 11.0)	1.65-1.62 (m)	1.62 (dm, 11.0)	1.62 (dm, 11.0)
9b	1.36 (dm, 11.0)	1.37-1.32 (m)	1.33 (dm, 11.0)	1.33 (dm, 11.0)
2’, 6’	7.80 (d, 8.5)	7.83 (d, 8.5)	7.94 (d, 8.5)	7.93 (d, 8.0)
3’, 5’	7.69 (d, 8.5)	7.66 (d, 8.5)	7.68 (d, 8.5)	7.69 (d, 8.0)
2’’, 6’’	7.79 (d, 8.0)	7.78 (d, 8.3)	7.80 (d, 8.0)	7.80 (d, 8.0)
3’’, 5’’	7.68 (d, 8.0)	7.68 (d, 8.3)	7.69 (d, 8.0)	7.67 (d, 8.0)

C	δ / ppm (J / Hz)
C	24	25	26	27
1	40.1	39.9	39.7	39.7
2	83.0	82.9	82.9	82.9
3	43.9	42.2	43.9	43.9
4	24.6	29.7	26.6	26.6
5	44.0	46.7	41.4	41.4
6	88.3	56.9	50.7	50.7
7	51.2	84.8	87.9	87.9
8	42.8	40.3	43.5	43.5
9	33.9	33.8	33.2	33.2
10	155.9	156.1	156.2	156.2
11	155.2	155.4	155.7	155.7
1’	132.8	132.8	132.8	132.8
2’, 6’	126.9	127.1	127.2	127.9
3’, 5’	125.8 (q, 3.8)	125.8 (q, 3.8)	125.8 (q, 3.8)	125.9 (q, 3.8)
4’	132.0 (q, 32.8)	131.9 (q, 32.8)	132.1 (q, 32.7)	131.5 (q, 32.6)
CF₃’	123.8 (q, 272.4)	123.8 (q, 272.1)	124.9 (q, 272.2)	123.9 (q, 272.1)
1’’	132.7	132.7	132.3	132.3
2’’, 6’’	126.9	126.9	126.9	126.9
3’’, 5’’	125.8 (q, 3.8)	125.7 (q, 3.7)	125.8 (q, 3.8)	125.8 (q, 3.7)
CF₃’’	123.8 (q, 272.4)	123.8 (q, 272.0)	124.8 (q, 272.4)	123.8 (q, 272.5)
4’’	131.5 (q, 32.7)	131.5 (q, 35.7)	131.3 (q, 32.6)	132.0 (q, 32.7)

Dipolarophile/C atom	Electric charge
Dipolarophile/C atom	C1	C2	C4/6	C3/C5	C8	C9/C12	C10	Site selectivity
5	-0.16	-0.11	-0.16	-0.144	-0.154	-0.106	-	C1/C2
8	-0.106	-0.159	-0.152	-0.154	-0.093	-0.234	-0.152	C1/C2
10	-	-	-0.104	-0.169	-0.086	-0.235	-	C8/C12
13	-0.159	-0.159	-0.159	-0.159	-	-0.159	-0.159	C9/C10
18	-0.150	-0.141	-0.150	-0.141	-	-	-	-
21 exo	-	-0.173	-	-0.176	-0.151	-0.113	-	C2/C3
21 endo	-	-0.172	-	-0.170	-0.145	-0.111	-	C2/C3

Compound	Linear growth inhibition / %
Compound	A. a.	B. c.	F. c.	P. c.	Rh. s.
6	0	78.7	24.0	2.4	0
7	10	0	0	0	11
11	0	15.6	0	11.1	0
12	13	0	4.4	0	0
19 + 20	-	73.0	38.0	12.0	11.0
14 + 15	17.4	20.0	0	11.1	30.0
16 + 17	10.9	28.9	0	37.8	18.0
22	26.0	28.0	0	0	24.0
23	13.0	4.4	0	11.1	0
24	4.3	8.9	11.1	17.8	0
25	15.2	31.1	0	22.2	0
26	0	11.1	4.4	4.4	0
27	0	8.9	0	15.6	0
Chlorothalonil^a a Reference compound. A. a.: Alternaria alternate; B. c.: Botrytis cinerea; F. c.: Fusarium culmorum; P. c.: Phytophtora cactorum; Rh. s.: Rhizoctonia solani.	-	80.0	38.0	61.0	88.0

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