7-C60-adduct of N,N-(tetrachlorophthaloyl)dehydroabietylamine

.

Scheme 1. Preparation of compound 5.

Table 1. ¹H- and ¹³C-NMR data, ¹H-¹H correlations in COSY, ROESY spectra and ¹H-¹³C correlations in HSQC, HMBC spectra for compound 5.

C	δC (ppm)	H	δH (ppm)	HSQC	HMBC	COSY	ROESY
1	39.48	1β	2.39 (br d, J = 11.9 Hz)	H-1β, 1α	H-20, 2, 3α	H-1α, 2	H-20, 11, 2, 1α
		1α	1.79–1.74 (m)			H-1β, 2	H-5, 11, 1β
2	18.18	2	1.85–1.79 (m, 2H)	H-2		H-3β, 3α, 1β, 1α	H-19, 3β, 3α, 1β
3	37.52	3β	1.58 (br d, J = 13.0 Hz)	H-3β, 3α	H-19, 18α, 18β	H-3α, 2	H-19, 3α, 2
		3α	1.53–1.47 (m)			H-3β, 2	H-5, 18α, 3β, 2
4	40.89	―	―	―	H-19, 5, 18α, 18β, 6β	―	―
5	48.67	5	1.97 (dd, J = 10.3, 9.2 Hz)	H-5	H-19, 20, 18α, 18β, 6α, 6β	H-6β, 6α	H-3α, 1α, 6α, 18α, 2
6	28.35	6β	3.65 (dd, J = 14.1, 10.5 Hz)	H-6β, 6α	C-6/H-5	H-5, 6α	H-19, 20, 6α
		6α	3.41 (dd, J = 14.1, 8.8 Hz)			H-5, 6β	H-5, 6β, 18α
7	44.61	―	―	―	H-6α, 6β, 14, 11	―	―
8	132.15	―	―	―	H-6β, 11,	―	―
9	150.35	―	―	―	H-14, 12, 20, 5	―	―
10	38.83	―	―	―	H-20, 5, 6α, 2, 11	―	―
11	123.40	11	7.43 (d, J = 8.1 Hz)	H-11	H-12	H-12	H-1β, 1α, 12
12	126.09	12	7.28 (dd, J = 8.1, 1.8 Hz)	H-12	H-15, 11, 14	H-11	H-15, 11, 16
13	145.43	―	―	―	H-16, 17, 15, 11	―	―
14	126.42	14	8.40 (d, J = 1.8 Hz)	H-14	H-12, 15	―	―
15	33.92	15	2.99 (septet, J = 6.7 Hz)	H-15	H-16, 17, 12, 14	H-16, 17	H-16, 17, 12
16	23.70	16	1.30 (d, J = 6.8 Hz, 3H)	H-16	H-15, 17,	H-15	H-15, 12
17	24.49	17	1.32 (d, J = 7.0 Hz, 3H)	H-17	H-15, 16	H-15	H-15
18	50.45	18β	3.88 (d, J = 13.6 Hz)	H-18β, 18α	H-19, 5	H-18α	H-18α, 19
		18α	3.59 (d, J = 13.6 Hz)			H-18β	H-18β, 5, 3α, 6α
19	18.89	19	1.31 (s, 3H)	H-19	H-5, 18α, 18β	―	H-20, 6β, 18β, 3β, 2
20	22.50	20	1.86 (s, 3H)	H-20	H-1α, 5	―	H-19, 6β, 1β
21,22	84.80	―	―	―	H-6α, 6β	―	―
	77.66	―	―	―	H-6α	―	―
1',6'	127.52	―	―	―	―	―	―
2',5'	129.76	―	―	―	―	―	―
3',4'	140.35	―	―	―	―	―	―
7',8'	164.51	―	―	―	H-18α, 18β	―	―
C60	150.74–137.82	―	―	―	―	―	―

Figure 2. ¹H-NMR spectrum of compound 5.

Figure 3. ¹³C-NMR spectrum of compound 5.

 5 as a dark brown solid (145 mg, 41%). IR ν_max/cm⁻¹: 3430, 2923, 2858, 1776, 1721, 1628, 1559, 1514, 1459, 1427, 1372, 1334, 1163, 1059, 893, 825, 740, 555, 526, 472; UV-vis (CHCl₃) λ_max (nm): 697.00, 493.00, 436.50; ¹H-NMR: δ 8.40 (d, J = 1.8 Hz, 1H), 7.43 (d, J = 8.1 Hz, 1H), 7.28 (dd, J = 8.1, 1.8 Hz, 1H), 3.88 (d, J = 13.6 Hz, 1H), 3.65 (dd, J = 14.1, 10.5 Hz, 1H), 3.59 (d, J = 13.6 Hz, 1H), 2.99 (septet, J = 6.7 Hz, 1H), 2.39 (br d, J = 11.9 Hz, 1H), 1.97 (dd, J = 10.3, 9.2 Hz, 1H), 1.86 (s, 3H), 1.85–1.79 (m, 2H), 1.79–1.74 (m, 1H), 1.58 (br d, J = 13.0 Hz, 1H), 1.53–1.47 (m, 1H), 1.32 (d, J = 7.0 Hz, 3H), 1.31 (s, 3H), 1.30 (d, J = 6.8 Hz, 3H); ¹³C-NMR: δ 164.51 (2C=O, imide), 150.74, 150.35, 149.89, 147.97, 147.53, 145.99, 145.92, 145.43, 145.27, 145.24, 145.21, 145.17, 145.02, 144.96, 144.89, 144.78, 144.68, 144.21, 144.19, 143.97, 143.87, 143.68, 143.25, 143.19, 143.16, 143.06, 143.01, 142.84, 142.76, 142.24, 142.18, 142.13, 142.06, 141.87, 141.40, 141.15, 141.04, 140.84, 140.35 (2C, -N(CO)₂C₆Cl₄), 140.22, 138.59, 138.51, 137.94, 137.82, 132.15, 129.76 (2C, -N(CO)₂C₆Cl₄), 127.52 (2C, -N(CO)₂C₆Cl₄), 126.42, 126.09, 123.40, 84.80, 77.66, 50.45, 48.67, 44.61, 40.89, 39.48, 38.83, 37.52, 33.92, 28.35, 24.49, 23.70, 22.50, 18.89, 18.18; MALDI-TOF MS (matrix: CHCA, reflectron negative) m/z 1269.4 M⁻(³⁵Cl₄), 1271.4 M⁻(³⁵Cl₃³⁷Cl), 1273.4 M⁻(³⁵Cl₂³⁷Cl₂), 1275.4 M⁻(³⁵Cl³⁷Cl₃); Anal. Calcd for C₈₈H₂₇Cl₄NO₂ (1271.97): C, 83.09; H, 2.14; N, 1.10. Found: C, 82.48; H, 2.20; N, 1.04.

Molecules 2012, 17(4), 4209-4218; doi:10.3390/molecules17044209

Synthesis and NMR Spectral Studies of the 7-C₆₀-Adduct of N,N-(Tetrachlorophthaloyl) Dehydroabietylamine

Zhi Zhou ^1,2,* and Zhongxiang Lin ¹

¹

College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China

²

College of Life and Environmental Sciences, Kaili University, Kaili, Guizhou 556011, China

*

Author to whom correspondence should be addressed; Email: Tel./Fax: +86-25-8542-7065.

Received: 4 March 2012; in revised form: 25 March 2012 / Accepted: 27 March 2012 / Published: 5 April 2012

Abstract

: The 7-C₆₀-adduct of N,N-(tetrachlorophthaloyl)dehydroabietylamine was synthesized for the first time and characterized by IR, UV-vis, mass and NMR spectral studies. The ¹H-NMR and ¹³C-NMR resonance signals of the new compound are unambiguously assigned by using homo- and heteronuclear 2D NMR spectroscopic techniques such as COSY, ROESY, HSQC and HMBC. The C₁ symmetric structure with 6,6-junction of compound was determined.

Keywords:

7-C₆₀-adduct of N,N-(tetrachlorophthaloyl)dehydroabietylamine; ¹H-NMR; ¹³C-NMR; 2D NMR; C₁ symmetric structure

 http://www.mdpi.com/1420-3049/17/4/4209/htm

///////