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Article

Synthesis of the Sex Pheromones of the Pine Caterpillar, Dendrolimus punctatus (Walker)

by
Chuanwen Lin
,
Sijie Ma
,
Xiao Sun
,
Qinghua Bian
and
Jiangchun Zhong
*
Department of Applied Chemistry, China Agricultural University, 2 West Yuanmingyuan Road, Beijing 100193, China
*
Author to whom correspondence should be addressed.
Reactions 2024, 5(4), 860-867; https://doi.org/10.3390/reactions5040045
Submission received: 21 September 2024 / Revised: 25 October 2024 / Accepted: 31 October 2024 / Published: 4 November 2024
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Abstract

:
The pine caterpillar, Dendrolimus punctatus (Walker), is a notorious forest pest. An efficient and convenient synthesis of the sex pheromones of this pest has been achieved. In our synthetic approach, a Wittig coupling of an aldehyde with an ester-bearing phosphonium salt was used to construct the Z-alkene, whereas the E-alkene was prepared via a stereoselective reduction of an alkyne with LiAlH4. The synthetic sex pheromones would be useful for integrated pest management of the pine caterpillar.

1. Introduction

The pine caterpillar, Dendrolimus punctatus (Walker), has become a notorious forest pest, which is widely distributed in China, Japan, Vietnam and India [1,2]. The larvae feed on the needles of various pines, such as the masson pine (Pinus massoniana), the slash pine (Pinus elliottii), and the Chinese pine (Pinus tabulaeformis) [3,4], whereas adult females mate and spawn on pine needles [5,6]. When the outbreak of D. punctatus occurred, thousands of pines were severely damaged [7,8], which caused huge economic and ecological losses [9]. The current controls rely mainly on insecticides [5,10], and this has led to insect resistance for emamectin benzoate, chlorpyrifos, cyhalothrin, and deltamethrin [11,12].
Compared to traditional pesticides, pheromone-based pest control has the advantages of being highly efficient, environmentally benign, and rarely causing insect resistance [13,14]. The sex pheromones produced by female D. punctatus were identified as (Z)-dodec-5-en-1-ol (1), (Z)-dodec-5-en-1-yl acetate (2), (5Z,7E)-dodeca-5,7-dien-1-ol (3), (5Z,7E)-dodeca-5,7-dien-1-yl acetate (4), and (5Z,7E)-dodeca-5,7-dien-1-yl propionate (5) (Figure 1) [15,16,17]. Due to their utility in trapping and monitoring D. punctatus [18,19], many organic chemists have studied the synthesis of these molecules. The previous synthesis mainly focused on Pd-CaCO3 catalyzed hydrogenation of an alkyne [20], (NCP) IrHCl-amine-EtOH catalyzed Z-selective reduction of an alkyne [21], cyclometalated ruthenium benzylidene catalyzed Z-selective cross-metathesis of a terminal alkene [22], zinc reduction of an enyne [23], Pd-catalyzed coupling of an alkenyl iodide with an alkynylstannane [24], and a Wittig reaction of a ω-hydroxyalkylphosphonium salt [25]. To seek out a more efficient, convenient, and cheaper synthesis of the sex pheromone of D. punctatus, herein, we have developed an alternative preparation of sex pheromones 1–5, and the key steps involved the Wittig coupling of an aldehyde with an ester-bearing phosphonium salt and the stereoselective reduction with LiAlH4 of an alkyne.

2. Materials and Methods

2.1. General Information

All non-aqueous reactions were performed under an argon atmosphere and using Schlenk techniques. Toluene, THF, CH2Cl2, and Et3N were dried over CaH2 and were distilled prior to use. All commercial reagents were used as received without further purification. 1H and 13C NMR spectra were recorded on a Bruker DP-X300 MHz spectrometer (Bruker, Billerica, MA, USA) at 300 and 75 MHz, and all chemical shifts were reported relative to tetramethylsilane (0.00 ppm) for 1H NMR and CDCl3 (77.16 ppm) for 13C NMR. High resolution mass (HRMS) analyses were conducted on an Agilent instrument with ESI-TOF MS technique (Agilent, Santa Clara, CA, USA).

2.2. Synthesis of (5-Ethoxy-5-oxopeptyl)triphenylphosphonium Bromide (7)

Ethyl 5-bromopentanoate (6) (2.091 g, 10 mmol) was dissolved in toluene (30 mL) at room temperature, triphenylphosphine (3.934 g, 15 mmol) was then added. The reaction mixture was heated to reflux and stirred vigorously for 24 h. Toluene was removed by a rotary evaporator, and the subsequent silica gel chromatography with an eluent of DCM/CH3OH 20:1 afforded (5-ethoxy-5-oxopentyl)triphenylphosphonium bromide (7) (4.242 g, 90% yield) as a colorless oil. 1H NMR (300 MHz, CDCl3) δ 7.88–7.74 (m, 15H), 4.02 (q, J = 7.1 Hz, 2H), 3.84–3.74 (m, 2H), 2.38 (t, J = 6.8 Hz, 2H), 2.03–1.96 (m, 2H), 1.77–1.72 (m, 2H), 1.17 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 172.56, 134.81 (d, J = 2.9 Hz), 133.31 (d, J = 9.9 Hz), 130.23 (d, J = 12.5 Hz), 117.79 (d, J = 85.5 Hz), 59.95, 33.02, 25.13 (d, J = 16.7 Hz), 22.28 (d, J = 50.5 Hz), 21.58 (d, J = 4.1 Hz), 13.86. HRMS (ESI-TOF): calcd. for C25H28O2BrNaP [M+Na]+ 493.09025, found 493.09521.

2.3. Synthesis of Ethyl (Z)-Dodec-5-enoate (9)

Phosphonium salt 7 (5.700 g, 12.09 mmol) was dissolved in THF (120 mL) at room temperature. After being cooled to −78 °C, sodium bis(trimethylsilyl)amide (6.1 mL, 2.0 M in THF, 12.20 mmol) was added via a syringe. The resulting mixture was maintained at −78 °C with a vigorous stirring for 1 h, followed by a dropwise addition of n-heptanal (8) (2.761 g, 24.18 mmol). Allowing the reaction mixture to warm to 25 °C and stir for 9 h, saturated aqueous NH4Cl solution (30 mL) was then added. Two phases were separated, and the aqueous phase was extracted with Et2O (3 × 40 mL). The ether extracts were combined with the organic phase and dried over anhydrous Na2SO4. Tetrahydrofuran and diethyl ether were removed by a rotary evaporator, and the subsequent silica gel chromatography with an eluent of petroleum ether/EtOAc 120:1 afforded ethyl (Z)-dodec-5-enoate (9) (1.986 g, 73% yield) as a pale-yellow oil. 1H NMR (300 MHz, CDCl3) δ 5.42–5.30 (m, 2H), 4.13 (q, J = 7.1 Hz, 2H), 2.30 (t, J = 7.5 Hz, 2H), 2.09–1.99 (m, 4H), 1.71–1.66 (m, 2H), 1.29–1.23 (m, 11H), 0.89 (t, J = 6.9 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 173.77, 131.23, 128.51, 60.26, 33.88, 31.88, 29.79, 29.09, 27.34, 26.67, 25.07, 22.75, 14.35, 14.17. HRMS (ESI-TOF): calcd. for C14H26O2Na [M+Na]+ 249.18250, found 249.18278.

2.4. Synthesis of (Z)-Dodec-5-en-1-ol (1)

LiAlH4 (0.167 g, 4.42 mmol) was added to anhydrous THF (5 mL) at room temperature, and the resulting suspension was cooled to 0 °C. Ethyl (Z)-dodec-5-enoate (9) (0.500 g, 2.21 mmol) in THF (5 mL) was then added via a syringe. Allowing reaction mixture to warm to 25 °C and stir for 8 h, saturated aqueous NH4Cl solution (5 mL) and MeOH (3 mL) were added. The resulting mixture was filtered, and the filter was rinsed with diethyl ether (30 mL). The ether rinse was combined with the filtrate, washed with brine (20 mL), and dried over anhydrous Na2SO4. Diethyl ether and tetrahydrofuran were removed by a rotary evaporator, and the subsequent silica gel chromatography with an eluent of petroleum ether/EtOAc 5:1 afforded (Z)-dodec-5-en-1-ol (1) (0.240 g, 59% yield) as a colorless oil. 1H NMR (300 MHz, CDCl3) δ 5.39–5.34 (m, 2H), 3.64 (t, J = 6.5 Hz, 2H), 2.10–1.98 (m, 4H), 1.69 (br s, 1H), 1.61–1.56 (m, 2H), 1.44–1.28 (m, 10H), 0.88 (t, J = 6.7 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 130.51, 129.43, 62.95, 32.49, 31.89, 29.82, 29.10, 27.37, 27.03, 25.99, 22.76, 14.18. HRMS (ESI-TOF): calcd. for C12H24ONa [M+Na]+ 207.17194, found 207.17207.

2.5. Synthesis of (Z)-Dodec-5-en-1-yl Acetate (2)

(Z)-Dodec-5-en-1-ol (1) (0.171 g, 0.93 mmol) was dissolved in anhydrous DCM (4 mL) at room temperature, followed by an addition of Et3N (0.564 g, 5.58 mmol). After being cooled to 0 °C, acetic anhydride (0.284 g, 2.79 mmol) was added dropwise via a syringe. Allowing the reaction solution to warm to 25 °C and stir for 8 h, water (5 mL) was added to quench the reaction. Two phases were separated, and the aqueous phase was extracted with DCM (3 × 5 mL). The dichloromethane extracts were combined with the organic phase, washed with brine (30 mL), and dried over anhydrous Na2SO4. Dichloromethane was removed by a rotary evaporator at 0 °C, and the subsequent silica gel chromatography with an eluent of petroleum ether/EtOAc 80:1 afforded (Z)-dodec-5-en-1-yl acetate (2) (0.181 g, 86% yield) as a pale-yellow oil. 1H NMR (300 MHz, CDCl3) δ 5.40–5.31 (m, 2H), 4.06 (t, J = 6.7 Hz, 2H), 2.10–1.98 (m, 7H), 1.69–1.59 (m, 2H), 1.46–1.28 (m, 10H), 0.87 (t, J = 6.9 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 171.03, 130.60, 129.03, 64.45, 31.83, 29.74, 29.02, 28.28, 27.29, 26.78, 26.08, 22.69, 20.91, 14.08. HRMS (ESI-TOF): calcd. for C14H26O2Na [M+Na]+ 249.18250, found 249.18275.

2.6. Synthesis of Hept-2-yn-1-ol (12)

Propargyl alcohol (10) (1.121 g, 20.00 mmol) was dissolved in anhydrous THF (40 mL) at room temperature, and HMPA (10.752 g, 60.00 mmol) was then added. The resulting mixture was cooled to −78 °C, followed by a dropwise addition of n-BuLi (16.7 mL, 2.4 M in n-hexane, 40.00 mmol) via a syringe. Allowing the mixture to warm to −30 °C and stir for 1 h, n-butyl bromide (11) (1.370 g, 10.00 mmol) was added dropwise. Then, the reaction mixture was warmed to 25 °C, and maintained at this temperature with a vigorous stirring for 9 h. Saturated aqueous NH4Cl solution (25 mL) was added to quench the reaction. Two phases were separated, and the aqueous phase was extracted with Et2O (3 × 25 mL). The ether extracts were combined with the organic phase and dried over anhydrous Na2SO4. Diethyl ether, tetrahydrofuran and n-hexane were removed by a rotary evaporator, and the subsequent silica gel chromatography with an eluent of petroleum ether/EtOAc 10:1 afforded hept-2-yn-1-ol (12) (0.909 g, 81% yield) as a colorless oil. 1H NMR (300 MHz, CDCl3) δ 4.25 (s, 2H), 2.25–2.18 (m, 2H), 1.90 (br s, 1H), 1.52–1.40 (m, 4H), 0.91 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3) 86.63, 78.43, 51.45, 30.78, 22.03, 18.51, 13.65. HRMS (ESI-TOF): calcd. for C7H13O [M+H]+ 113.09609, found 113.09721.

2.7. Synthesis of (E)-Hept-2-en-1-ol (13)

LiAlH4 (0.759 g, 2.00 mmol) was added to anhydrous THF (5 mL) at room temperature. The resulting suspension was cooled to 0 °C, and hept-2-yn-1-ol (12) (0.112 g, 1.00 mmol) in THF (3 mL) was then added via a syringe. Allowing the reaction mixture to warm to 25 °C and stir for 9 h, it was cooled to 0 °C. Saturated NH4Cl aqueous solution (5 mL) and MeOH (3 mL) were added to quench the reaction. The resulting mixture was filtered, and the filter was rinsed with diethyl ether (30 mL). The filtrate was extracted with Et2O (3 × 5 mL). The ether extracts were combined with the filtrate and dried over anhydrous Na2SO4. Diethyl ether and tetrahydrofuran were removed by a rotary evaporator, and the subsequent silica gel chromatography with an eluent of petroleum ether/EtOAc 5:1 afforded (E)-hept-2-en-1-ol (13) (0.0936 g, 82% yield) as a colorless oil. 1H NMR (300 MHz, CDCl3) δ 5.74–5.57 (m, 2H), 4.06 (d, J = 4.9 Hz, 2H), 2.24 (br s, 1H), 2.07–2.01 (m, 2H), 1.36–1.29 (m, 4H), 0.90 (t, J = 6.9 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 133.45, 129.13, 63.78, 32.08, 31.52, 22.41, 14.07. HRMS (ESI-TOF): calcd. for C7H15O [M+H]+ 115.11174, found 115.11179.

2.8. Synthesis of Ethyl (5Z,7E)-Dodeca-5,7-dienoate (14)

To a two-neck 50 mL Schlenk flask we added 4Å MS (0.200 g) and PDC (0.489 g, 1.30 mmol) at room temperature. (E)-Hept-2-en-1-ol (13) (0.114 g, 1.00 mmol) in DCM (5 mL) was then added via a syringe. After the reaction mixture was maintained at 25 °C with a vigorous stirring for 9 h, it was filtered. The filter was rinsed with CH2Cl2 (30 mL). The dichloromethane rinse was combined with the filtrate, washed with brine (3 × 10 mL), and dried over anhydrous Na2SO4. Dichloromethane was removed by a rotary evaporator to give the crude (E)-hept-2-enal as a pale-yellow liquid.
To another two-neck 50 mL Schlenk flask we added phosphonium salt 7 (1.414 g, 3.00 mmol) and anhydrous THF (10 mL) at room temperature. After being cooled to −78 °C, sodium bis(trimethylsilyl)amide (1.75 mL, 2.0 M in THF, 3.50 mmol) was added via a syringe. The resulting mixture was maintained at −78 °C with a vigorous stirring for 2 h, followed by a dropwise addition of the crude (E)-hept-2-enal (0.114 g, 1.00 mmol) in THF (2 mL). Allowing the reaction mixture to warm to 25 °C and stir for 20 h, saturated aqueous NH4Cl solution (5 mL) was added. Two phases were separated, and the aqueous phase was extracted with Et2O (3 × 10 mL). The ether extracts were combined with the organic phase and dried over anhydrous Na2SO4. Tetrahydrofuran and diethyl ether were removed by a rotary evaporator, and the subsequent silica gel chromatography with an eluent of petroleum ether/EtOAc 100:1 afforded ethyl (5Z,7E)-dodeca-5,7-dienoate (14) (0.157 g, 70% yield over two steps) as a pale yellow oil. 1H NMR (300 MHz, CDCl3) δ 6.31–6.22 (m, 1H), 6.02–5.94 (m, 1H), 5.72–5.62 (m, 1H), 5.30–5.24 (m, 1H), 4.13 (q, J = 7.1 Hz, 2H), 2.31 (t, J = 7.5 Hz, 2H), 2.22–2.19 (m, 2H), 2.10–2.04 (m, 2H), 1.74–1.69 (m, 2H), 1.37–1.31 (m, 4H), 1.25 (t, J = 7.2 Hz, 3H), 0.90 (t, J = 6.0 Hz, 3H). 13C NMR (75 MHz, CDCl3)δ 173.74, 135.42, 129.87, 128.40, 125.49, 60.32, 33.81, 32.68, 31.66, 27.10, 25.05, 22.40, 14.37, 14.04. HRMS (ESI-TOF): calcd. for C14H24O2Na [M+Na]+ 247.1668516740, found 247.16805.

2.9. Synthesis of (5Z,7E)-Dodeca-5,7-dien-1-ol (3)

LiAlH4 (0.759 g, 2.00 mmol) was added to anhydrous THF (5 mL) at room temperature, and the resulting suspension was cooled to 0 °C. Ethyl (5Z,7E)-dodeca-5,7-dienoate (14) (0.224 g, 1.00 mmol) in THF (3 mL) was then added via a syringe. Allowing reaction mixture to warm to 25 °C and stir for 9 h, saturated aqueous solution NH4Cl (5 mL) was added. Two phases were separated, and the aqueous phase was extracted with Et2O (3 × 5 mL). The ether extracts were combined with the organic phase and dried over anhydrous Na2SO4. Tetrahydrofuran and diethyl ether were removed by a rotary evaporator, and the subsequent silica gel chromatography with an eluent of petroleum ether/EtOAc 10:1 afforded (5Z,7E)-dodeca-5,7-dien-1-ol (3) (0.159 g, 87% yield) as a colorless oil. 1H NMR (300 MHz, CDCl3) δ 6.33–6.24 (m, 1H), 5.96 (dd, J = 12.9, 8.9 Hz, 1H), 5.66 (dt, J = 14.5, 7.0 Hz, 1H), 5.29 (dt, J = 10.6, 7.5 Hz, 1H), 3.63 (t, J = 7.0 Hz, 2H), 2.21–2.08 (m, 4H), 1.93 (br s, 1H), 1.62–1.56 (m, 2H), 1.47–1.33 (m, 6H), 0.90 (t, J = 7.0 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 135.05, 129.43, 129.13, 125.57, 62.79, 32.63, 32.36, 31.63, 27.45, 25.94, 22.35, 13.99. HRMS (ESI-TOF): calcd. for C12H23O [M+H]+ 183.17434, found 183.17523.

2.10. Synthesis of (5Z,7E)-Dodeca-5,7-dien-1-yl Acetate (4)

(5Z,7E)-Dodeca-5,7-dien-1-ol (3) (0.182 g, 1.00 mmol) was dissolved in anhydrous DCM (3 mL) at room temperature, and Et3N (0.606 g, 6.00 mmol) was added. The resulting mixture was cooled to 0 °C, and acetyl chloride (0.235 g, 3.00 mmol) in DCM (2 mL) was added dropwise. Allowing reaction mixture to warm to 25 °C and stir for 9 h, water (5 mL) was added. Two phases were separated, and the aqueous phase was extracted with Et2O (3 × 5 mL). The ether extracts were combined with the organic phase and dried over anhydrous Na2SO4. Diethyl ether and dichloromethane were removed by a rotary evaporator at 0 °C, and the subsequent silica gel chromatography with an eluent of petroleum ether/EtOAc 100:1 afforded (5Z,7E)-dodeca-5,7-dien-1-yl acetate (4) (0.209 g, 93% yield) as a pale-yellow oil. 1H NMR (300 MHz, CDCl3) δ 6.32–6.23 (m, 1H), 6.00–5.93 (m, 1H), 5.69–5.64 (m, 1H), 5.27 (dt, J = 10.7, 7.5 Hz, 1H), 4.07 (t, J = 6.6 Hz, 2H), 2.21–2.07 (m, 4H), 2.04 (s, 3H), 1.71–1.63 (m, 2H), 1.37–1.33 (m, 6H), 0.90 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3) 171.26, 135.24, 129.37, 129.08, 125.54, 64.53, 32.67, 31.66, 28.30, 27.32, 26.15, 22.38, 21.07, 14.03. HRMS (ESI-TOF): calcd. for C14H25O2 [M+H]+ 225.18491, found 225.18529.

2.11. Synthesis of (5Z,7E)-Dodeca-5,7-dien-1-yl Propionate (5)

According to the similar procedure for sex pheromone 4, the esterification of (5Z,7E)-dodeca-5,7-dien-1-ol (3) (0.182 g, 1.00 mmol) with propionyl chloride (0.278 g, 3.00 mmol) provided (5Z,7E)-dodeca-5,7-dien-1-yl propionate (5) (0.224, 94% yield) as a pale-yellow oil. 1H NMR (300 MHz, CDCl3) δ 6.33–6.24 (m, 1H), 6.00–5.93 (m, 1H), 5.72–5.62 (m, 1H), 5.27 (dt, J = 10.7, 7.6 Hz, 1H), 4.08 (t, J = 6.6 Hz, 2H), 2.31 (q, J = 7.6 Hz, 2H), 2.21–2.09 (m, 4H), 1.70–1.63 (m, 2H), 1.47–1.34 (m, 6H), 1.14 (t, J = 7.6 Hz, 3H), 0.90 (t, J = 6.9 Hz, 3H). 13C NMR (75 MHz, CDCl3) δ 174.62, 135.20, 129.35, 129.10, 125.55, 64.34, 32.66, 31.65, 28.35, 27.71, 27.32, 26.16, 22.37, 14.01, 9.25. HRMS (ESI-TOF): calcd. for C15H27O2Na [M+H+Na]+ 262.19033, found 262.19059.

3. Results and Discussion

3.1. Synthesis of Sex Pheromones 1 and 2

Our synthesis commenced with the preparation of sex pheromones 1 and 2 (Scheme 1). The reaction of ethyl 5-bromopentanoate (6) with Ph3P in toluene provided phosphonium salt 7 in 90% yield [26,27], followed by a Wittig coupling with n-heptanal (8) to produce ethyl (Z)-dodec-5-enoate (9) [28,29]. The reduction with LiAlH4 converted olefinic ester 9 to sex pheromone 1 [30,31], and following direct acetylation with acetic anhydride afforded sex pheromone 2 in 86% yield [32].

3.2. Synthesis of Sex Pheromones 3, 4 and 5

Having achieved the preparation of sex pheromones 1 and 2, we next synthesized sex pheromones 3, 4, and 5 (Scheme 2). In the presence of HMPA, the alkylation of an alkynyllithium, prepared in situ from propargyl alcohol (10) and n-BuLi, with n-butyl bromide (11) led to hept-2-yn-1-ol (12) (81% yield) [33,34]. The stereoselective reduction of alkynol 12 with LiAlH4 furnished (E)-hept-2-en-1-ol (13) [35,36]. The oxidation of enol 13 with pyridinium dichromate (PDC) resulted in the formation of (E)-hept-2-enal [37], which was reacted with phosphonium salt 7 to afford ethyl (5Z,7E)-dodeca-5,7-dienoate (14) (70% yield over two steps) [27,28]. Finally, dienylester 14 was directly reduced to sex pheromones 3 in 87% yield [30], and the subsequent esterification with acetyl chloride and propionyl chloride gave sex pheromones 4 and 5 in 93% and 94% yield, respectively [38,39].

4. Conclusions

In summary, we have achieved an efficient and convenient synthesis of the sex pheromone of the pine caterpillar. Our synthetic strategy mainly includes a Wittig coupling of an aldehyde with an ester-bearing phosphonium salt and the stereoselective reduction with LiAlH4 of an alkyne. The synthetic sex pheromones could be used to monitor and trap D. punctatus.

5. Patents

The patent (CN 109456182A, China) entitled “Synthesis method of (5Z,7E)-dodeca-5,7-dien-1-ol, its acetate and propionate ester” by our group resulted in the work reported in this manuscript.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/reactions5040045/s1, Figure S1: 1H NMR Spectrum of (5-ethoxy-5-oxopentyl)triphenylphosphonium bromide (7) (300 MHz, CDCl3). Figure S2: 13C NMR Spectrum of (5-ethoxy-5-oxopentyl)triphenylphosphonium bromide (7) (75 MHz, CDCl3). Figure S3: 1H NMR Spectrum of ethyl (Z)-dodec-5-enoate (9) (300 MHz, CDCl3). Figure S4: 13C NMR Spectrum of ethyl (Z)-dodec-5-enoate (9) (75 MHz, CDCl3). Figure S5: 1H NMR Spectrum of (Z)-dodec-5-en-1-ol (1) (300 MHz, CDCl3). Figure S6: 13C NMR Spectrum of (Z)-dodec-5-en-1-ol (1) (75 MHz, CDCl3). Figure S7: 1H NMR Spectrum of (Z)-dodec-5-en-1-yl acetate (2) (300 MHz, CDCl3). Figure S8: 13C NMR Spectrum of (Z)-dodec-5-en-1-yl acetate (2) (75 MHz, CDCl3). Figure S9: 1H NMR Spectrum of hept-2-yn-1-ol (12) (300 MHz, CDCl3). Figure S10: 13C NMR Spectrum of hept-2-yn-1-ol (12) (75 MHz, CDCl3). Figure S11: 1H NMR Spectrum of (E)-hept-2-en-1-ol (13) (300 MHz, CDCl3). Figure S12: 13C NMR Spectrum of (E)-hept-2-en-1-ol (13) (75 MHz, CDCl3). Figure S13: 1H NMR Spectrum of ethyl (5Z,7E)-dodeca-5,7-dienoate (14) (300 MHz, CDCl3). Figure S14: 13C NMR Spectrum of ethyl (5Z,7E)-dodeca-5,7-dienoate (14) (75 MHz, CDCl3). Figure S15: 1H NMR Spectrum of (5Z,7E)-dodeca-5,7-dien-1-ol (3) (300 MHz, CDCl3). Figure S16: 13C NMR Spectrum of (5Z,7E)-dodeca-5,7-dien-1-ol (3) (75 MHz, CDCl3). Figure S17: 1H NMR Spectrum of (5Z,7E)-dodeca-5,7-dien-1-yl acetate (4) (300 MHz, CDCl3). Figure S18: 13C NMR Spectrum of (5Z,7E)-dodeca-5,7-dien-1-yl acetate (4) (75 MHz, CDCl3). Figure S19: 1H NMR Spectrum of (5Z,7E)-dodeca-5,7-dien-1-yl propionate (5) (300 MHz, CDCl3). Figure S20: 13C NMR Spectrum of (5Z,7E)-dodeca-5,7-dien-1-yl propionate (5) (75 MHz, CDCl3).

Author Contributions

Conceptualization, J.Z.; methodology, C.L., S.M. and X.S.; writing—original draft preparation, C.L.; writing—review and editing, Q.B. and J.Z.; funding acquisition, J.Z. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Key Technology Research and Development Program of China (No. 2023YFD1800900).

Data Availability Statement

The data presented in this article are available in the Supplementary Materials.

Conflicts of Interest

The authors declare no conflicts of interest.

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Reactions 05 00045 g001
Figure 1. Sex pheromones of the pine caterpillar.
Figure 1. Sex pheromones of the pine caterpillar.
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Scheme 1. Synthesis of sex pheromones 1 and 2.
Scheme 1. Synthesis of sex pheromones 1 and 2.
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Scheme 2. Synthesis of sex pheromones 3, 4 and 5.
Scheme 2. Synthesis of sex pheromones 3, 4 and 5.
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Lin, C.; Ma, S.; Sun, X.; Bian, Q.; Zhong, J. Synthesis of the Sex Pheromones of the Pine Caterpillar, Dendrolimus punctatus (Walker). Reactions 2024, 5, 860-867. https://doi.org/10.3390/reactions5040045

AMA Style

Lin C, Ma S, Sun X, Bian Q, Zhong J. Synthesis of the Sex Pheromones of the Pine Caterpillar, Dendrolimus punctatus (Walker). Reactions. 2024; 5(4):860-867. https://doi.org/10.3390/reactions5040045

Chicago/Turabian Style

Lin, Chuanwen, Sijie Ma, Xiao Sun, Qinghua Bian, and Jiangchun Zhong. 2024. "Synthesis of the Sex Pheromones of the Pine Caterpillar, Dendrolimus punctatus (Walker)" Reactions 5, no. 4: 860-867. https://doi.org/10.3390/reactions5040045

APA Style

Lin, C., Ma, S., Sun, X., Bian, Q., & Zhong, J. (2024). Synthesis of the Sex Pheromones of the Pine Caterpillar, Dendrolimus punctatus (Walker). Reactions, 5(4), 860-867. https://doi.org/10.3390/reactions5040045

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