Study On The Synthesis Of Novel Chiral Fluorescence Derivatizing Reagents Deriving From Methyl 13,14-diaminodeisopropyldehydroabietate

Dehydroabietic acid (DAA) is one of important renewable resource. It is widely used in many fields such as paint, adhesives, printing ink, papermaking, rubber, food additive,biological product, etc. DAA is a natural chiral compound with three chiral carbon atom and a reactive carboxy group. Like some natural drug, it has a aromatic diterpene structure with three ring . For above reasons, DAA might be hopefully modified to some multifunctional derivatives and novel fluorescence derivatization reagents through constructing aromatic or heteroaromatic ring on DAA's skeleton.Part I, starting from dehydroabietic acid which was purified from disproportionated rosin, two important intermedias, Methyl 12-bromo-13, 14-dinitro- deisopropyldehydroabietate (MBDDDA) and Methyl 13, 14-dinitro- deisopropyldehydroabietate were synthesized through methylation, bromination, nitration and reduce. Then two phena-zines (methyl(1R,4aS,18aS)-1,4a- dimethyl-1, 2, 3, 4, 4a, 17, 18, 18a-octahydro-dibenzo [a, c] naphtho [2, 1-h] phenazine- 1-carbixylate and methyl (1R, 4aS, 18aS) -1, 4a-dimethyl- 1, 2, 3, 4, 4a, 17, 18, 18a- octahydronaphtho [2, 1-h] dipyrido [3, 2-a: 2, 3-c] phenazine-1-carboxylate) were synthesized by the reaction between MDDDA phen-5, 6-dione. Compared with DAA's methyl ester, both the products'maximal excitation wavelengths and emission wavelengths are bathochromic shifted with with fluorescentλex/λem of 406-420nm/450-460nm and their excitation wavelengths meet with our demand. Then, a chiral fluorescence derivatization reagent was synthesized through two steps.Part II, methyl (1R, 4aS, 16aS) -1, 4a-dimethyl-1, 2, 3, 4, 4a, 15, 16, 16a- octahydroacenaphtho [2, 1-f] quinoxaline-1-carboxylate was synthesized from Methyl 13, 14- diaminodeisopropyl- dehydroabietate and acenaphthenequinone. Methyl- (1S, 4aS, 15aS) -6-bromo-1, 4a-dimethl- 2, 3, 4, 4a, 8, 14, 15, 15a-octahydro-1H-indolo [3, 2-b] naphtho [2, 1-f] quinoxaline-1-carboxylate and Methyl-(1S, 4aS, 15aS)-6-bromo-1, 4a-dimethl-2, 3, 4, 4a, 8, 14, 15, 15a- octahydro-1H-indolo [2, 3-b] naphtho [2, 1-f] quinoxaline-1-carboxylate were synthesized through the reaction between MBDDDA and isatin. The three quinoxaline emit fluorescence of 440-460 nm if excited by a violet light ranging 380-420 nm.Part III, a pair of isomers, methyl (1s, 4aR, 17aS)-1, 4a-dihydroxy-8-oxo-1, 2, 3, 4, 4a, 16, 17, 17a-octahydro-8H-benzo [de] phenanthro [1', 2': 4, 5] imidazo [1, 2-a] isquinoline-1-carboxylate and methyl (1s, 4aR, 17aS)-1, 4a-dihydroxy -8-oxo-1, 3, 4, 4a, 8, 16, 17, 17a-oc- tahydro-2H-benzo [de] phenanthro [2', 1': 4,5] imidazo [1, 2-a] quinoline-1-carboxylate which have good fluorescenceλex /λem of 450/515nm were synthesized by the reaction between 1,8-naphthalic anhydride and Methyl 13, 14-diaminodeisopropyl-dehydroabietate.Part IV, a series of benzimidazoles were synthesized using a simple and efficient procedure from MBDDDA and aldehydes.In summary, 14 new compounds were synthesized and characterized by IR, NMR and MS in this paper. We provide a novel and convenient synthetic strategy of chiral fluorescence derivatizing reagents . The relation between constructure of derivatizations from dehydroabietate and their properties in ultraviolet and fluorescence were studied in detail. All that laid the groundwork for future exploitation of chiral fluorescence derivatizing reagents . Our study shows that DAA's fluorescence properties were greatly improved through constructing heteroaromatic ring such as phenazine, quinoxaline and benzimidazoles on DAA's skeleton. We hope that the chiral fluorescence derivatizing reagents which derive from DAA can be used in seperation of chiral amino acids and chiral drugs.