Synthesis and Herbicidal Activities of Bifunctional Acetic Acid Ester Derivatives of Monoterpene Oxabicyclodiol

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1 Vol ~ 190 Chinese Journal of Synthetic Chemistry No ~ 190 * R 4R ⅠⅠ 4 3a ~ 3d 1 H NMR 13 C NMRFT-IR HR-MS rn2 n1 3a ~ 3d 1 5 mmolr = 7 7 h3a ~ 3d 21. 6% 15. 6% 37. 9% 24. 9% 1 5 mmolr = 4 7 h3a ~ 3d 50. 7% 36. 6% 7. 84% 4. 86% 1 3a ~ 3d 1 3a ~ 3d 5 mmol L a ~ 3d 55. 1% 86. 0% 84. 2% 91. 3% 97. 5% 55. 1% 76. 5% 92. 8% 94. 8% 98. 4% 3R 4R TQ351 A DI /j. cnki. cjsc Synthesis and Herbicidal Activities of Bifunctional Acetic Acid Ester Derivatives of Monoterpene xabicyclodiol HUANG Dao-zhanZHU Shou-jiLAN Hong-yun LEI Fu-hongHUANG Zhong-jing Guangxi Key Laboratory of Chemistry and Engineering of Forest Products College of Chemistry and Chemical EngineeringGuangxi University for NationalitiesNanning China AbstractFour novel acetic acid ester derivatives3a ~ 3dwere synthesized by the reaction of 3R 4R trimethyl-6-oxabicyclo octane-3 4-diol1with acetyl chloride2by one-pot method and then purified. The structures were characterized by 1 H NMR 13 C NMRFT-IR and HR-MS. Effects of material ratior n2 n1 and reaction time on the relative concentration of 3a ~ 3d were investigated. The resluts showed that the relative concentration of 3a ~ 3d were 21. 6% 15. 6% 37. 9% and 24. 9% under the condition of 1 5 mmol r = 7 and reflux for 7 h. The relative concentration of 3a ~ 3d were 55. 1% 86. 0% 84. 2% 91. 3% and 97. 5% under the condition of 1 5 mmolr = 4 and reflux for 7 h. The herbicidal activities of 1 and 3a ~ 3d were tested by dish dipping method. The results showed that 1 and 3a ~ 3d exhibited obvious inhibition activities against the growth of annual ryegrass root and shoot. The inhibition rate of 1 and 3a ~ 3d against root growth at 5 * GXNSFA huangdaozhan@ gxun. edu. cn

2 186 Vol mmol L - 1 were 55. 1% 86. 0% 84. 2% 91. 3% and 97. 5% respectively. The inhibition rate of 1 and 3a ~ 3d against shoot elongation at 5 mmol L - 1 were 55. 1% 76. 5% 92. 8% 94. 8% and 98. 4% respectively. Keywords 3R 4R trimethyl-6-oxabicyclo octane-3 4-diolacetyl chloridebifunctional monoterpene oxabicyclodiol derivativesynthesisherbicidal activity WRS-1B Bruker Avance 600 MHz CDCl TMS Nicolet Magna KBr 2- Shimadzu GC-14B Perkin Elmer Clarus500 MAT 95XP 8- LRH-250-GSI R 4R α mmol 500 mmol ml 0. 5 h mmol 50 ml 7 1 h 1 mol 3-4- L ml 1. 5 mol L - 1 Na 2 C ml ⅠⅠ V V = GC 3a ~ 3dScheme 1 1 H NMR 3a3b 13 C NMRFT-IR HR-MS A3c3d 3b 3a 1 3a ~ 3d Comp a b c d R 1 R 2 H - b' a' - b a - Scheme 1 - f' e' d' - b' a' c' e f d - b a c - b' a' 0. 5 ml 1 ml R 4S a 3R 4S b A 200 mlv V = b 3R 4S c 3R 4S-3- -4

3 C C C d 3a 22% m. p ~ H NMR δ4. 99 ~ 5. 02ddJ = 4. 8 Hz3. 6 Hz 1H3-H 3. 93s1H4-H ~ 2. 30d J = Hz1H5-H ~ 2. 14m3H1- H2-H eq 8-H eq 2. 06s3Ha'-H 1. 93d J = 3. 0 Hz1H8-H ax ~ 1. 48m1H2-1 H NMR δ5. 66s 1Ha -H ~ 5. 15dd H ax 1. 39s3H4-H 1. 18s3H10-H J = 6. 0 Hz5. 4 Hz1H3-H ~ 4. 87d 1. 17s3H9-H 13 C NMR δ C b' J = 6. 0 Hz1H5-H s3ha'-h C C C C C C C 10 d f -H ~ m1h1-h ~ C C C a' C 4 IR ν cm - 1 HR-MS m /zcalcd for C 12 H 20 4 M found b 16% 1 H NMR δ5. 06 ~ 5. 09dd J = 6. 6 Hz4. 8 Hz1H3-H ~ 4. 82d J = 6. 0 Hz1H5-H ~ d1h8- H eq 2. 03s3Ha -H ~ 2. 02m1H 1-H ~ 1. 93d1H2-H eq ~ dj = 6. 0 Hz1H8-H ax ~ dd J = 2. 4 Hz9. 0 Hz1H2-H ax 1. 43s3H4- H1. 40 s3h10-h s3h9-h 13 C NMR δ C a C a' C C C C C C C C C a' C a C 4 3b ~ 3d C 2 IR ν cm - 1 HR-MS m /zcalcd for C 14 H 22 5 M found c % m. p ~ H NMR δ5. 68s 1Ha'-H ~ 5. 15dd m1h1-h ~ 1. 97d1HJ = 3. 0 Hz 2-H eq ~ t1hj = Hz8- H ax ~ 1. 54m1H2-H ax 1. 47s3H 4-H 1. 41s3H10-H 1. 17s3H9-H 13 C NMR δ C c' C C C f' C C C C C a IR ν cm - 1 HR-MS m /zcalcd for C 18 H 26 7 M found d 25% m. p ~ ~ 2. 17m1H8-H eq ~ 2. 08s6H dj = Hz1H2-H eq 1. 67s1H 8-H ax ~ m1h2-h ax s 3H4-H 1. 42s3H10-H 1. 18s3H9- H 13 C NMR δ C c C e C b' C b C a C C C C C C C d C f C C C C C a' IR ν cm - 1 HR-MS m /zcalcd for C 18 H 26 7 M found a mmol L -1 DMF a ~ 3d h = 9 cm 10 ml 3 J = 6. 6 Hz4. 8 Hz1H3-H ~ 4. 91d DMF 80 J = 6. 0 Hz1H5-H s3ha -H ~ ddj = 2. 4 Hz1. 8 Hz1H d H eq ~ 2. 04s 6Hc' d'-h ~ GC r n2 n1 1 3a ~ C b C b' C a' C 7 3d

4 188 Vol GC 1r 1 5 mmol 1. 2 r 3a ~ 3d 1 Table 1 r 1 * r 3a ~ 3d Effects of r on relative concentration of 3a ~ 3d /% 3a 3b 3c 3d h * 1 5 mmolr = n2 n a 3b3c 3d 1 r 3a ~ 3d 3a 3b3c 3d r = 1 3ar = h3a ~ 3d 3a3b ~ 3d 16% 50. 7% 36. 6% 7. 84% 4. 86% r 3a 1 3-3b 3c 3d 2 3a r = 4 3a 3b 3-4- r 3c 3d 3b3b 2 3c 3d 3a 3b H NMR H NMR 3a ~ 3d CH 3 7-CH 3 7-CH δ ~ a3- δ c 3d d f-hδ ~ b 2 3b α ~ Hδ δ ~ δ 2 3c 3d 2 13 C NMR 3b 13 C NMR 3a ~ 3d α- r > 23c 3d mmolr = t3a ~ 3d 2 2 t /h Table 2 * 3a ~ 3d Effects of reaction time on relative concentration of 3a ~ 3d /% 3a 3b 3c 3d * 1 5 mmolr = 4 1 a -Hδ C b δ 170 C d C f δ C b δ C c

5 Table 3 1 3a ~ 3d Inhibition rate of 1 and 3a ~ 3d on annual ryegrass c / /% mmol L a 3b 3c 3d δ a ~ 3d 4-7- δ 82 ~ δ IR IR 3a - H mmol L mmol L a ~ 3d cm - 1 3b ~ 3d - H 8. 2% 20. 2% 26. 7% cm - 1 ~ cm % 29. 2% 55. 1% 86. 0% cm % 91. 3% 97. 5% 13. 9% 21. 1% 51. 7% 26. 9% 29. 7% 4GC 55. 1% 76. 5% 92. 8% 94. 8% 98. 4% c 1 Figure 1 R t /min 3a ~ 3d GC GC spectra of 3a ~ 3d 3 1 3a ~ 3d c c mmol L - 1 3a ~ 3d 100% 3 1 3a ~ 3d a ~ 3d 3a ~ 3d 15 3d 3c 3d 3c 3 4 3a ~ 3d 1 5 mmolr = 7 7 h3a ~ 3d 21. 6% 15. 6% 37. 9% 24. 9% 1 3a ~ 3d GC mmolr = 4 7 h 5 min 3a ~ 3d 50. 7% 36. 6% 2 5 min 7. 84% 4. 86% 1 3a ~ 3d a ~ 3d min min min min

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