CN103965091A - Preparation of 2-(2,3,6,7-tetramethoxy-9-phenanthrmethylmethyl)pyrrole - Google Patents

Preparation of 2-(2,3,6,7-tetramethoxy-9-phenanthrmethylmethyl)pyrrole Download PDF

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CN103965091A
CN103965091A CN201310027118.9A CN201310027118A CN103965091A CN 103965091 A CN103965091 A CN 103965091A CN 201310027118 A CN201310027118 A CN 201310027118A CN 103965091 A CN103965091 A CN 103965091A
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tetramethoxy
luxuriant
pyrroles
rich
fragrance
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CN103965091B (en
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梁华中
徐西之
邓玉智
钱永志
巩绪干
汪清民
孙新
吴瑞磊
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JIANGSU LANFENG BIOCHEMICAL CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/333—Radicals substituted by oxygen or sulfur atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyrrole Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention relates to preparation of 2-(2,3,6,7-tetramethoxy-9-phenanthrmethylmethyl)pyrrole. 2-(2,3,6,7-tetramethoxy-9-phenanthrmethylformyl)pyrrole reacts with di-tert-butyl dicarbonate (i.e., (Boc)2O) to produce N-tert-butyloxycarbonyl-2(2,3,6,7-tetramethoxy-9-phenanthrmethylformyl)pyrrole; and then N-tert-butyloxycarbonyl-2(2,3,6,7-tetramethoxy-9-phenanthrmethylformyl)pyrrole reacts with NaBH4 to produce 2-(2,3,6,7-tetramethoxy-9-phenanthrmethylmethyl)pyrrole.

Description

2-(the luxuriant and rich with fragrance methyl of 2,3,6,7-tetramethoxy-9-) pyrroles's preparation
Technical field
The present invention relates to 2-(the luxuriant and rich with fragrance methyl of 2,3,6,7-tetramethoxy-9-) pyrroles's preparation.
Background technology
The viroses of plant are very serious Plant diseasess, prevent and treat very difficultly, have the title of " plant cancer ".The eruption and prevalence of viral diseases of plants is very extensive, and disaster is very serious.Nearly all vegetables, food crop, fruit tree etc. all infect virus disease, make agriculture production be subject to huge loss, reduce product quality, have seriously promoted the generation of other physiological disturbance of plant.The practical kind of effective and gratifying plant virus inhibitor is little at present, and especially still less, wherein the preventive effect of Ningnanmycin is best for the therapeutic medicament of special efficacy.Conventional have following three commercialization kinds: Ningnanmycin, field using dosage is 100gai/hm 2, be 50%～60% to tobacco mosaic disease prevention effect, there is good preventive effect, result for the treatment of is not good; Virazole, field using dosage is 600gai/hm 2, be 30～60% to the preventive effect of plant virus (tobacco mosaic virus (TMV), cucumber mosaic virus, potato virus X, marmor upsilon etc.); Virus A, field using dosage is 600gai/hm 2, be 50% to tobacco mosaic disease prevention effect.Professor Song Baoan of Guizhou University has formulated viral star, and field using dosage is 300gai/hm 2.Therefore, very urgent to the needs of efficient, safe Control of Plant Virus Disease medicament.
Organic element chemistry National Key Laboratory of Nankai University finds that the leaching thing of the Niuxin Pozicao that is distributed widely in the husky desert belt of NORTHWEST CHINA drought has high activity to very harmful tobacco mosaic virus (TMV) (TMV) first, further biological activity tracking and chemically separated result of study show: in this grass, the active substance of anti-TMV is phenanthroindolizididerivative pyridine alkaloid, and main active ingredient is antofine.This active substance under 1.0 μ g/mL concentration to the inhibiting rate of tobacco mosaic virus (TMV) up to 60%, this activity than any plant virus inhibitor of having seen bibliographical information exceeds 1-2 the order of magnitude.But Niuxin Pozicao is born in desert and barren hillside, be per nnial herb, be the plant of preventing and fixing sand; Moreover the content of anti-TMV active ingredient antofine in Niuxin Pozicao is very low, the content of antofine in Niuxin Pozicao crude extract is only 0.2% left and right.So, from Niuxin Pozicao, extract antofine and be restricted for plant protection.Antofine illumination is unstable; Antofine is water-soluble very poor, and this has a strong impact on its application in plant protection.In order to address the above problem, Nankai University is taking active ingredient antofine alkaloid as guide, carry out chemosynthesis, carry out structure of modification and modification, the Control of Plant Virus Disease medicament NK-007 that formulate out good light stability, there is water-soluble, activity is higher, the results of field plot on 2 years seven ground shows: the effect of NK-007 control tobacco, capsicum, tomato virus disease is far away higher than two contrast medicament Ningnanmycins and viral A, the preventive effect of 10 grams/ha of NK-007 and 100 grams/ha of Ningnanmycins, 600
Gram/ha viral A is suitable, to crop without poisoning phenomenon, on other non-target organism without impact.
The CA number of logging in of NK-007 (Universal Chinese character name: phenanthridines poison is clear): 1203657-55-9, chemical name: the malate of tylophorine, molecular formula: C 28h 33nO 9, structural formula is as follows:
Nankai University has applied for NK-007 and derivative thereof, the synthetic Chinese invention patent with applying, for example, ZL200610129555.1 and ZL 201110050446.1 disclose phenanthroindolizididerivative pyridine and phenanthro-quinoline in western piperidine derivatives and the application of salt on agricultural chemicals thereof, CN101875657A discloses the application of tylophorine Alkaloid organic acid salt derivative on agricultural chemicals, and ZL 200710058173.9 discloses the preparation of phenanthroindolizididerivative derivative.Nankai University by the compound of NK-007 and derivative thereof, syntheticly transfer Jiangsu Lam Fung Biological Chemical Co., Ltd with the exclusive right to use of applying the above-mentioned patent relating to, by Jiangsu Lam Fung Biological Chemical Co., Ltd exclusively develop, produce without competition, exclusive dealing.
ZL 200710058173.9 discloses the preparation of phenanthroindolizididerivative derivative, for 2, synthesizing of 3,6,7-tetramethoxy phenanthroindolizididerivative pyridine, comprise the steps: first with 3, the condensation reaction of 4-dimethoxyphenylacetic acid and Veratraldehyde obtains 2,3-bis--(3,4-Dimethoxyphenyl) vinylformic acid, then obtained 2,3,6 with iron trichloride oxidative coupling, 7-tetramethoxy phenanthrenecarboxylic acid, this acid is reacted and is obtained 2,3 with thionyl chloride, and 6, the luxuriant and rich with fragrance formyl chloride of 7-tetramethoxy, at SnCl 4exist lower this acyl chlorides to react with pyrroles and generate 2-(the luxuriant and rich with fragrance formyl radical of 2,3,6,7-tetramethoxy-9-) pyrroles, use NaBH 4reducing carbonyl obtains 2-(2, the luxuriant and rich with fragrance methyl of 3,6,7-tetramethoxy-9-) pyrroles, obtain 2-(2 with Pd-C catalytic hydrogenation reduction pyrroles again, the luxuriant and rich with fragrance methyl of 3,6,7-tetramethoxy-9-) Pyrrolidine, finally close ring with formaldehyde and obtain 2, the pyridine of 3,6,7-tetramethoxy phenanthroindolizididerivative.
Jiangsu Lam Fung Biological Chemical Co., Ltd, in the time carrying out the synthesising process research of 2,3,6,7-tetramethoxy phenanthroindolizididerivative pyridine, finds 2-(the luxuriant and rich with fragrance formyl radical of 2,3,6,7-tetramethoxy-9-) the pyrroles NaBH of ZL200710058173.9 protection 4reducing carbonyl generates 2-(2,3,6, the luxuriant and rich with fragrance methyl of 7-tetramethoxy-9-) pyrroles's method, there are the following problems: 2-(2,3, the luxuriant and rich with fragrance formyl radical of 6,7-tetramethoxy-9-) solubleness of pyrroles in Virahol is very low, so need to add a large amount of Virahols to dissolve 2-(2,3, the luxuriant and rich with fragrance formyl radical of 6,7-tetramethoxy-9-) pyrroles, therefore, the quantity of solvent that the method needs is very big, and the utilization ratio of reactor is very low; In the time of amplification quantity, even if find to add a large amount of Virahols, react always incomplete, 2-(the luxuriant and rich with fragrance formyl radical of 2,3,6,7-tetramethoxy-9-) pyrroles's low conversion rate, yield significantly declines; 2-(the luxuriant and rich with fragrance formyl radical of 2,3,6,7-tetramethoxy-9-) pyrroles's less stable, in the process of reflux, as nitrogen protection is bad, reaction solution color is very dark, particularly evident when amplification quantity; Product 2-(the luxuriant and rich with fragrance methyl of 2,3,6,7-tetramethoxy-9-) pyrroles need to cross column chromatography.
In order to address the above problem; Jiangsu Lam Fung Biological Chemical Co., Ltd has carried out by 2-(2; 3; the luxuriant and rich with fragrance formyl radical of 6,7-tetramethoxy-9-) pyrroles makes raw material, synthetic 2-(2; 3; the luxuriant and rich with fragrance methyl of 6,7-tetramethoxy-9-) pyrroles's Study of New Method, finally invent this novel method.
Summary of the invention
The object of this invention is to provide 2-(the luxuriant and rich with fragrance methyl of 2,3,6,7-tetramethoxy-9-) pyrroles's novel preparation method.
2-of the present invention (the luxuriant and rich with fragrance methyl of 2,3,6,7-tetramethoxy-9-) pyrroles's synthetic route following (equation 1).Preparation method comprises the steps: first with 2-(the luxuriant and rich with fragrance formyl radical of 2,3,6,7-tetramethoxy-9-) pyrroles and tert-Butyl dicarbonate (i.e. (Boc) 2o) reaction generates N-tertbutyloxycarbonyl-2-(the luxuriant and rich with fragrance formyl radical of 2,3,6,7-tetramethoxy-9-) pyrroles, then with NaBH 4reaction obtains 2-(the luxuriant and rich with fragrance methyl of 2,3,6,7-tetramethoxy-9-) pyrroles.
Equation 1
Wherein, the patented method of 2-(the luxuriant and rich with fragrance formyl radical of 2,3,6,7-tetramethoxy-9-) pyrroles's synthetic employing ZL 200710058173.9.
The advantage of novel method: 2-(2, 3, 6, the luxuriant and rich with fragrance formyl radical of 7-tetramethoxy-9-) pyrroles generates first with high yield N-tertbutyloxycarbonyl-2-(2 after BOC protection, 3, 6, the luxuriant and rich with fragrance formyl radical of 7-tetramethoxy-9-) pyrroles, N-tertbutyloxycarbonyl-2-(2, 3, 6, the luxuriant and rich with fragrance formyl radical of 7-tetramethoxy-9-) pyrroles is a new compound, solvability and stability are fine, and then carry out sodium borohydride reduction, speed of response is accelerated, reaction times reduces, transformation efficiency improves, quantity of solvent reduces, product content improves, do not need to carry out again column chromatography, the total recovery of two steps is higher than the method for patent ZL 200710058173.9.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer and more definite, below in conjunction with embodiment, the present invention is described in further detail, describe and only limit to better explain the present invention herein, be not intended to limit the present invention.
Embodiment 1:N-tertbutyloxycarbonyl-2-(the luxuriant and rich with fragrance formyl radical of 2,3,6,7-tetramethoxy-9-) pyrroles's is synthetic:
In 1000 mL four-hole reaction flasks, add successively 41 grams of 2-(the luxuriant and rich with fragrance formyl radical of 2,3,6,7-tetramethoxy-9-) pyrroles, 600 mL acetonitriles, 4.0 grams of DMAP, nitrogen replacement, adds 40 grams of tert-Butyl dicarbonates (i.e. (Boc) 2o), stirring reaction 24 hours at 20 DEG C.Slough acetonitrile, add saturated sodium bicarbonate solution, regulate pH=9, suction filtration, dries, and obtains 50.0 grams of N-tertbutyloxycarbonyl-2-(the luxuriant and rich with fragrance formyl radical of 2,3,6,7-tetramethoxy-9-) pyrroles, yield: 99.86%, and fusing point: 145-146 DEG C. 1H NMR(400 MHz，CDCl 3)：δ8.28(s，1H)，7.94(s，1H)，7.82(s，1H)，7.78(s，1H)，7.50(s，1H)，7.21(s，1H)，6.68(d，J＝1.8 Hz，1H)，6.26(t，J＝3.2 Hz，1H)，4.15(s，3H)，4.14(s，3H)，4.01(s，6H)，1.39(s，9H)； 13C NMR(100 MHz，CDCl 3)δ 187.4，151.2，149.3，149.0，148.9，135.2，131.5，130.4，127.3，126.8，125.2，124.4，124.0，122.8，110.3，109.3，106.9，102.6，85.0，56.1，56.0，55.9，27.5；IR(KBr，cm -1)：3115，3067，2980，2941，2836，1748，1626，1512，1470，1435，1313，1256，1203，1159，1134，1049，844，778，746；MS(ESI)：[2M+Na]1005.1；HRMS(ESI)calcd for C 28H 30NO 7(M+H) +：492.2017，found：492.2018。
Embodiment 2:2-(the luxuriant and rich with fragrance methyl of 2,3,6,7-tetramethoxy-9-) pyrroles's is synthetic:
In 1000 mL four-hole reaction flasks, add 10.0 grams of N-tertbutyloxycarbonyl-2-(2,3,6; the luxuriant and rich with fragrance formyl radical of 7-tetramethoxy-9-) pyrroles, 11 grams of sodium borohydrides, 2 grams of Tetrabutyl amonium bromides; 500 mL newly steam Virahol, stir, and are heated to back flow reaction 4 hours.Slough Virahol, add 500 mL methylene dichloride and 130 mL water, dilute hydrochloric acid regulates pH=6, separatory, and precipitation, dries, and obtains 8.0 grams of solids, content 98.56%, yield 86.22%.Fusing point: 220-222 DEG C. 1H NMR(300 MHz，CDCl 3)δ 8.02(br，1 H)，7.70(s，1H)，7.66(s，1 H)，7.35(s，1H)，7.34(s，1H)，7.09(s，1H)，6.62-6.63(m，1H)，6.16-6.18(m，2H)，4.36(s，2H)，4.05(s，6H)，3.96(s，3H)，3.88(s，3H)； 13C NMR(75 MHz，CDCl 3)δ 149.0，148.9，148.6，130.9，130.1，126.2，125.5，125.0，124.8，124.0，116.9，108.4，108.1，106.3，105.1，103.2，102.8，56.0，55.9，55.8，55.7，32.7；IR(KBr，cm -1)3376，3267，3006，2904，2831，1612，1510，1460，1431，1249，1191，1140，1031，981，828，763，712，647，581，509；MS(EI)m/z 377(M +，100)，346(6)，311(8)，189(10)，80(7)；HRMS(ESI)m/z calcd for C 23H 24NO 4[M+H] +378.1700found378.1702.
Embodiment 3:2-(the luxuriant and rich with fragrance methyl of 2,3,6,7-tetramethoxy-9-) pyrroles's synthetic (using the method for patent ZL200710058173.9)
In 5000 mL reaction flasks, add 30 grams of 2-(2,3,6,7-tetramethoxy-9-luxuriant and rich with fragrance formyl radical) pyrroles, 30 grams of sodium borohydrides and 3500 mL Virahols, N 2the lower mixture reflux of protection 24 hours.In reaction solution, add 1500mL methylene dichloride and 400 mL water, separatory, organic phase is washed with saturated brine, anhydrous magnesium sulfate drying.Precipitation, column chromatography (eluent: CH 2cl 2: ethyl acetate: sherwood oil (60-90 DEG C)=15: 1: 1 volume ratios) obtain 16 grams of white solids, yield is 55%, fusing point: 220-222 DEG C.

Claims (2)

1. a 2-(2; 3; 6; the luxuriant and rich with fragrance methyl of 7-tetramethoxy-9-) pyrroles's preparation method; it is characterized in that comprising the following step shown in following equation 1: first with 2-(2; the luxuriant and rich with fragrance formyl radical of 3,6,7-tetramethoxy-9-) pyrroles and tert-Butyl dicarbonate (i.e. (Boc) 2o) reaction generates N-tertbutyloxycarbonyl-2-(the luxuriant and rich with fragrance formyl radical of 2,3,6,7-tetramethoxy-9-) pyrroles, then with NaBH 4reaction obtains 2-(the luxuriant and rich with fragrance methyl of 2,3,6,7-tetramethoxy-9-) pyrroles, equation 1:
2. 2-claimed in claim 1 (the luxuriant and rich with fragrance methyl of 2,3,6,7-tetramethoxy-9-) pyrroles's preparation method, is characterized in that N-tertbutyloxycarbonyl-2-(the luxuriant and rich with fragrance formyl radical of 2,3,6,7-tetramethoxy-9-) pyrroles.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN101189968A (en) * 2006-11-23 2008-06-04 南开大学 Phenanthroindolizidine and phenanthroquinolizidine derivatives and applications of salts in pesticides
CN101348483A (en) * 2007-07-17 2009-01-21 南开大学 Preparation of phenanthroindolizidine derivative
JP2012153661A (en) * 2011-01-27 2012-08-16 Kao Corp Hair growth inhibitor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101189968A (en) * 2006-11-23 2008-06-04 南开大学 Phenanthroindolizidine and phenanthroquinolizidine derivatives and applications of salts in pesticides
CN101348483A (en) * 2007-07-17 2009-01-21 南开大学 Preparation of phenanthroindolizidine derivative
JP2012153661A (en) * 2011-01-27 2012-08-16 Kao Corp Hair growth inhibitor

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KAI-LIANG WANG等: "Iron(III) chloride-based mild synthesis of phenanthrene and its application to total synthesis of phenanthroindolizidine alkaloids", 《TETRAHEDRON》 *
ROBERT GREENHOUSE等: "Synthesis of Alkylpyrroles by the Sodium Borohydride Reduction of Acylpyrroles1", 《THE JOURNAL OF ORGANIC CHEMISTRY》 *
王开亮，等: "菲并吲哚里西啶生物碱及其盐衍生物的生物活性研究", 《农药学学报》 *

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