CN1884277A - Dibenzanthracene, dinaphthopyran and dibenzanthracene, dinaphtho spiropyran analog compound and its preparation - Google Patents

Dibenzanthracene, dinaphthopyran and dibenzanthracene, dinaphtho spiropyran analog compound and its preparation Download PDF

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CN1884277A
CN1884277A CN 200610014049 CN200610014049A CN1884277A CN 1884277 A CN1884277 A CN 1884277A CN 200610014049 CN200610014049 CN 200610014049 CN 200610014049 A CN200610014049 A CN 200610014049A CN 1884277 A CN1884277 A CN 1884277A
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arh
dinaphtho
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carbon
dinaphthopyran
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CN100432067C (en
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王佰全
王斌
李敏雄
徐善生
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Nankai University
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Abstract

The invention relates to dibenz, naphthopyrans and dibenz and dibenz spiropyran compound, and the method for preparing the same. Said method comprises: dibenzofuran or naphthofurans reacting with lithium with molar ration being 1:2-2.4, opening loop, reacting with aldehyde, ketone, ester or amide at temperature of -70 to -80 Deg. C, the molar ratio between dibenzofuran or naphthofurans and aldehyde, ketone, ester or amide is 1:0.7-1, dewatering and closing loop, and getting final product. The invention is characterized by cheap raw material, simple process, high productivity, and multiple kinds of products.

Description

Dibenzo, dinaphthopyran and dibenzo, dinaphtho spiro-pyrans compounds and preparation
Technical field
The present invention relates to a kind of dibenzo, dinaphthopyran and dibenzo, dinaphtho spiro-pyrans compounds and preparation method thereof.
Background technology
Pyran compounds is the very important organic heterocyclic molecule of a class, has a wide range of applications in a lot of fields.Wherein, the non-benzopyrans compounds that functional group replaces be the synthesis of natural product important intermediate (Danishefsk, S.J.Aldrich.Acta 1986,19,59; Schmidt, R.R.Acc.Chem.Res.1986,19,250).Therefore benzo, naphtho-pyrans compounds have been subjected to people's great attention because practical application is more widely arranged.Benzopyrans compounds is that a class has bioactive compound, for this compounds at pharmaceutically application existing a lot of report (Evans, J.M.; Stemp, G.Chem.Ber.1991,27,439; Attwood, M.R.; Jones, P.S.; Paciorek, P.B.; Redshaw, S.Life Sci.1991,48,803; Attwood, M.R.; Churcher, I.; Dunsdon, R.M.; Hurst, D.V.; Jones, P.S.Tetrahedron Lett.1991,32,811; Bergmann, R.; Eiermann, V.; Gericke, R.J.Med.Chem.1990,33,2759 etc.).Photochromic and thermochromism can take place greatly in benzo, aphthopyrans and benzo, naphtho-spiro-pyrans compounds on the other hand, therefore they have been widely used in aspect (Guglielmetti, R.J. such as light-sensitive sunglasses, electronic display system, optical switch and photo-memory material; Crano, J.C.Organic Photochromic and Thermochromic Compounds, Plenum Press, NewYork, 1998).
With respect to above-mentioned several compounds, for the report of dibenzo, dinaphthopyran compounds and research seldom, and do not have for the report of dibenzo, dinaphtho spiro-pyrans compounds at all.The method of now having reported for preparing dibenzo, dinaphthopyran compounds not only raw material is not easy to obtain, the step complexity, and total recovery is low, and the kind of this two compounds that can prepare seldom (Huang, C.-G.; Bereridge, K.A.; Wan, P.J.Am.Chem.Soc.1991,113,7676; Bringmann, G.; Schoner, B.; Peters, K.; Peters, E.; Von Schnering, H.G.Liebigs Ann.Chem.1994,439), this has just limited the research of people for these several compounds greatly, but in fact these several compounds have huge using value.For example, the natural product cannabinol is exactly a kind of dibenzopyrans compounds (Kogan, N.M.; Rabinowitz, R.; Levi, P.; Gibson, D.; Sandor, P.; Schlesinger, M.; Mechoulam, R.J.Med.Chem.2004,47,3800), it is a kind of narcotic that is widely used.American G.B.Schuster (J.Am.Chem.Soc.1998,120,12619) deep research has been carried out in a kind of reversible photoresponse of dinaphthopyran compounds, proposed it and probably be applied to the photoswitch that nematic liquid crystal and cholesteryl liquid crystal are changed mutually.
Therefore, we openly prepare the achievement in research of a series of dibenzo, dinaphthopyran and dibenzo, dinaphtho spiro-pyrans compounds here.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing a series of dibenzo, dinaphthopyran and dibenzo, dinaphtho spiro-pyrans compounds by diphenylene-oxide (dibenzofuran) and one step of dinaphtho furans.
The general formula of dibenzopyrans and dibenzo spiro-pyrans compounds is (I):
R wherein 1, R 2: hydrogen atom, contain 1 to 20 carbon aliphatics substituting group, aromatic substituents, contain the aliphatics substituting group or the aromatic substituents of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom; R 1, R 2Can Cheng Huan, be aliphatics substituting group, the aromatic substituents that contains 1 to 20 carbon, aliphatics substituting group or the aromatic substituents that contains 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom; R 1, R 2Can be identical, also can be different.
The general formula of dinaphthopyran and dinaphtho spiro-pyrans compounds is (II):
R wherein 1, R 2: hydrogen atom, contain 1 to 20 carbon aliphatics substituting group, aromatic substituents, contain the aliphatics substituting group or the aromatic substituents of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom; R 1, R 2Can Cheng Huan, be aliphatics substituting group, the aromatic substituents that contains 1 to 20 carbon, aliphatics substituting group or the aromatic substituents that contains 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom; R 1, R 2Can be identical, also can be different.
The preparation method of described dibenzopyrans and dibenzo spiro-pyrans compounds, dinaphthopyran and dinaphtho spiro-pyrans compounds is: by diphenylene-oxide or dinaphtho furans and lithium by 1: the 2-2.4 molar ratio reaction, open loop, react with aldehyde, ketone, ester or acid amides at-70 ℃ to-80 ℃ then, the mol ratio of diphenylene-oxide or dinaphtho furans and aldehyde, ketone, ester or acid amides is 1: 0.7-1, dehydration closed-loop forms corresponding dibenzo, dinaphthopyran and dibenzo, dinaphtho spiro-pyrans compounds again.
The synthesis step of dibenzopyrans and dibenzo spiro-pyrans compounds is: with diphenylene-oxide, Tetramethyl Ethylene Diamine and lithium refluxed in ether 24 hours,-70 ℃ to-80 ℃ add aldehyde, ketone, ester or acid amides down, reaction rises to room temperature gradually, and room temperature reaction is after 12 hours, hydrolysis, pickling, dehydration is purified through separating, and can obtain corresponding product.
The synthesis step of dinaphthopyran and dinaphtho spiro-pyrans compounds is: with dinaphtho furans and lithium stirring at room 24 hours in ether,-70 ℃ to-80 ℃ add aldehyde, ketone, ester or acid amides down, reaction rises to room temperature gradually, behind the room temperature reaction 12 hours, hydrolysis, the acidifying dehydration is purified through separating, and can obtain corresponding product.
Its synthetic route such as Fig. 1, Fig. 2.
1-20 is the route synthetic compound by Fig. 1, also is the structural formula of compound among the embodiment
Figure A20061001404900051
Wherein, compound 1-16 is the dibenzopyrans compounds, and 17-20 is a dibenzo spiro-pyrans compounds.
21-33 is the route synthetic compound by Fig. 2, also is the structural formula of compound among the embodiment
Wherein, compound 21-29 is the dinaphthopyran compounds, and 30-33 is a dinaphtho spiro-pyrans compounds.
The application of described dibenzopyrans and dibenzo spiro-pyrans compounds, dinaphthopyran and dinaphtho spiro-pyrans compounds is the application on medicine and photochromic material.
The beneficial effect of present method is that raw material is cheap and easy to get, and step is simple, the productive rate height, and the kind of dibenzo, dinaphthopyran and the dibenzo that can prepare, dinaphtho spiro-pyrans compounds is a lot.
Description of drawings
Fig. 1 is the synthetic route of dibenzopyrans and dibenzo spiro-pyrans compounds
Fig. 2 is the synthetic route of dinaphthopyran and dinaphtho spiro-pyrans compounds
Outstanding substantive distinguishing features of the present invention and unusual effect can be embodied from following example, but they do not impose any restrictions the present invention.
Embodiment
Embodiment 1
Compound 1-19's is synthetic:
In the 100mL there-necked flask of magneton is housed, add 0.153g (22mmol) lithium, 1.680g (10mmol) diphenylene-oxide, 3.30mL (22mmol) Tetramethyl Ethylene Diamine and 50mL exsiccant ether, reflux 24 hours.Add 0.59mL (8mmol) acetone down at-78 ℃, reaction rises to room temperature gradually, and stirring is spent the night.Slowly add the hydrolysis of 3N dilute hydrochloric acid then, separatory adds 20mL concentrated hydrochloric acid, stirring at room 2 hours, separatory, water CH in organic phase 2Cl 2Extract (20mL * 4), merge organic phase, wash with water, add anhydrous Na to neutrality 2SO 4Dry.Except that desolvating, cross Al with Rotary Evaporators 2O 3Post gets colorless oil 1.23g, productive rate 73%.The synthetic method of compound 2-19 and compound 1 are similar.Compound 1-19's 1H NMR, 13C NMR, MS, EA, mp and productive rate see Table 1-4.
Embodiment 2
Synthesizing of compound 20:
In the 100mL there-necked flask of magneton is housed, add 0.153g (22mmol) lithium, 1.680g (10mmol) diphenylene-oxide, 3.30mL (22mmol) Tetramethyl Ethylene Diamine and 50mL exsiccant ether, reflux 24 hours.Add 1.402g (8mmol) 1,3 down at-78 ℃, 3-trimethylammonium-2-indolone, reaction rises to room temperature gradually, and stirring is spent the night.Decompressing and extracting solvent and Tetramethyl Ethylene Diamine add the 50mL ether again, slowly add the hydrolysis of 3N dilute hydrochloric acid, separatory, organic phase is washed (20mL * 3) with 3N dilute hydrochloric acid again, merges water, slowly adds NaOH solution to neutral, there are a large amount of solids to separate out, filter, the solid CH that obtains 2Cl 2With the normal hexane recrystallization, get 2.04g lightpink crystal.Compound 20 1H NMR, 13CNMR, MS, EA, mp and productive rate see Table 1-4.
Embodiment 3
Compound 21-32's is synthetic:
In the 100mL there-necked flask of magneton is housed, add 0.153g (22mmol) lithium, 2.680g (10mmol) dinaphtho furans and 50mL exsiccant ether, stirring at room 24 hours.Add 0.59mL (8mmol) acetone down at-78 ℃, reaction rises to room temperature gradually, and stirring is spent the night.Slowly add the hydrolysis of 3N dilute hydrochloric acid next day, and separatory adds 20mL concentrated hydrochloric acid, stirring at room 2 hours, separatory, water CH in organic phase 2Cl 2Extract (20mL * 4), merge organic phase, wash with water, add anhydrous Na to neutrality 2SO 4Dry.Remove with Rotary Evaporators then and desolvate, cross Al 2O 3Post gets colorless solid 1.79g, productive rate 72%.The synthetic method of compound 22-32 and compound 21 are similar.Compound 21-32's 1H NMR, 13C NMR, MS, EA, mp and productive rate see Table 1-4.
Embodiment 4
Synthesizing of compound 33:
In the 100mL there-necked flask of magneton is housed, add 0.153g (22mmol) lithium, 2.680g (10mmol) dinaphtho furans and 50mL exsiccant ether, stirring at room 24 hours.Add 1.402g (8mmol) 1,3 down at-78 ℃, 3-trimethylammonium-2-indolone, reaction rises to room temperature gradually, and stirring is spent the night.Slowly add the hydrolysis of 3N dilute hydrochloric acid next day, separatory, and organic phase is washed (20mL * 3) with 3N dilute hydrochloric acid, merges water, slowly adds NaOH solution to neutral, has a large amount of solids to separate out, and filters, with solid CH 2Cl 2With the normal hexane recrystallization, get the 2.84g pale yellow crystals, productive rate 83%.Compound 33 1HNMR, 13C NMR, MS, EA, mp and productive rate see Table 1-4.
Table 1 compound 1-33's 1H NMR data
Comp. 1H NMR(400MHz，in CDCl 3，ppm)(δ)
1 1.71(s，6H，CH 3)，7.03-7.10(m，2H，ArH)，7.28-7.41(m，4H，ArH)， 7.77-7.80(m，2H，ArH)
2 1.63(t，3H，CH 2)，1.69-1.73(m，2H，CH 2)，1.80-1.93(m，4H，CH 2)，2.13(d，J＝ 12.8Hz，2H，CH 2)，7.01-7.05(m，2H，ArH)，7.22-7.37(m，4H，ArH)，7.73(d， J＝6.8Hz，2H，ArH)
3 1.52-1.66(m，4H，CH 2)，1.71-1.77(m，2H，CH 2)，1.85-1.93(m，2H，CH 2)， 1.96-2.03(m，2H，CH 2)，2.21-2.27(m，2H，CH2)，6.97-7.03(m，2H，ArH)， 7.20-7.35(m，4H，ArH)，7.71(d，J＝7.6Hz，2H，ArH)
4 0.89(s，9H，CH 3)，1.25-1.35(m，2H，CH 2)，1.79-1.86(m，4H，CH 2)，2.35(d，J＝ 13.6Hz，2H，CH 2)，6.95(d，J＝8Hz，1H，ArH)，7.02(t，1H，ArH) 7.21-7.39(m，3H，ArH)，7.53(d，J＝7.2Hz，1H，ArH)，7.70-7.73(m，2H，ArH)
5 1.54(d，J＝12.4Hz，2H，Ada H)，1.74(s，2H，Ada H)，1.80(d，J＝13.2Hz，2H， AdaH)，1.93(s，2H，AdaH)，2.10(d，J＝13.2Hz，2H，AdaH)，2.36(s，2H， AdaH)，2.53(d，J＝12.4Hz，2H，AdaH)，7.03-7.07(m，2H，ArH)，7.25-7.38(m， 3H，ArH)，7.69(d，J＝7.6Hz，1H，ArH)，7.75-7.77(m，2H，ArH)
6 2.05(s，3H，CH 3)，6.96(t，1H，ArH)，7.04(d，J＝7.6Hz，1H，ArH)，7.17-7.44(m， 9H，ArH)，7.66(d，J＝8Hz，1H，ArH)，7，76(d，J＝7.6Hz，1H，ArH)
7 6.72(d，J＝8Hz，1H，ArH)，6.95(t，1H，ArH)，7.05(d，J＝8Hz，1H，ArH)， 7.16-7.27(m，12H，ArH)，7.41(t，1H，ArH)，7.66(d，J＝8Hz，1H，ArH)
8 6.20(s，1H，CH)，6.89(d，J＝7.6Hz，1H，ArH)，7.04-7.10(m，2H，ArH)， 7.24-7.29(m，2H，ArH)，7.38-7.45(m，6H，ArH)，7.78-7.81(m，2H，ArH)
9 2.02(s，3H，CH 3)，3.73(s，3H，OCH 3)，6.75(d，J＝8.8Hz，2H，ArH)， 6.94-7.01(m，2H，ArH)，7.17-7.26(m，5H，ArH)，7.33(t，1H，ArH)，7.41(t，1H， ArH)，7.66(d，J＝7.6Hz，1H，ArH)，7.75(d，J＝7.6Hz，1H，ArH)
10 6.06(d，J＝3.2Hz，1H，FurH)，6.26(d，J＝1.6Hz，1H，furH)，6.32(s，1H，CH)， 7.02-7.13(m，3H，ArH)，7.23-7.26(m，1H，ArH)，7.32(t，1H，FurH)7.45(t， 3H，ArH)，7.77-7.82(m，1H，ArH)
11 cis：6.40(s，1H，CH＝CH)，6.44(s，1H，CH＝CH)，6.82(s，1H，CH＝CH) 6.91-6.96(m，2H，ThiopheneH)，7.05(t，1H，ArH)，7.14(d，J＝8Hz，1H， ThiopheneH)，7.24-7.50(m，10H，ArH)，7.75(d，J＝8Hz，1H，ArH)，7.84(d，J＝ 7.6Hz，1H，ArH) trans：6.82(s，1H，CH＝CH)，6.86(s，1H，CH＝CH)，6.91-6.96(m，2H， ThiopheneH)，7.05(t，1H，ArH)，7.14(d，J＝8Hz，1H，ThiopheneH)， 7.24-7.50(m，10H，ArH)，7.75(d，J＝8Hz，1H，ArH)，7.84(d，J＝7.6Hz，1H， ArH)
12 cis：6.12(s，1H，CH＝CH)，6.16(s，1H，CH＝CH)，1.91(s，3H，CH 3)，6.16(s，1H， FurH)，6.31(t，1H，FurH)，7.03(t，2H，ArH)，7.23-7.43(m，ArH，FurH)， 7.73-7.79(m，1H，ArH) trans：6.39(s，1H，CH＝CH)，6.43(s，1H，CH＝CH)，1.91(s，3H，CH 3)，6.16(s， 1H，FurH)，6.31(t，1H，FurH)，7.03(t，2H，ArH)，7.23-7.43(m，ArH，FurH)， 7.73-7.79(m，1H，ArH)
13 2.25-2.32(m，1H，CH 2)，2.67-2.74(m，1H，CH 2)，2.89-2.96(m，1H，CH 2)， 3.14-3.21(m，1H，CH 2)，6.77(d，J＝7.6Hz，1H，ArH)，6.95(d，J＝8Hz，1H， ArH)，7.07(t，1H，ArH)，7.18-7.31(m，3H，ArH)，7.35-7.39(m，4H，ArH)， 7.81(d，J＝7.6Hz，2H，ArH)
14 1.86(s，3H，CH 3)，4.46(s，9H，FcH)，6.83-7.25(m，6H，ArH)，7.68(s，2H，ArH)
15 3.98-4.19(m，9H，FcH)5.98(s，1H，CH)7.02-7.37(m，6H，ArH)7.73(s， 2H，ArH)
16 6.59(d，J＝7.6Hz，1H，ArH)，6.92(d，J＝8Hz，1H，ArH)，7.06(t，1H，ArH)， 7.12-7.19(m，3H，ArH)，7.22-7.29(m，2H，ArH)，7.34-7.41(m，3H，ArH)， 7.69(d，J＝7.6Hz，2H，ArH)，7.89(d，J＝3.2Hz，1H，ArH)，7.90(d，J＝3.6Hz， 1H，ArH)
17 6.28(d，J＝9.6Hz，1H，CH＝CH)6.77(d，J＝8Hz，1H，CH＝CH) 6.96-7.30(m，7H，ArH)7.40-7.57(m，3H，ArH)7.95(t，2H，ArH)
18 6.39(d，J＝10Hz，1H，CH＝CH)，6.89(d，J＝8Hz，1H，CH＝CH)，6.97(d，J＝ 8.8Hz，1H，ArH)，7.15(t，1H，ArH)，7.25(t，1H，ArH)，7.40-7.44(m，2H，ArH)， 7.52-7.60(m，3H，ArH)，7.69(d，J＝8.8Hz，1H，ArH)，7.78-7.84(m，1H，ArH)， 7.93-7.98(m，2H，ArH)，8.18(d，J＝8.4Hz，1H，ArH)
19 6.90(d，J＝8Hz，2H，ArH)，7.15-7.35(m，8H，ArH)，7.54-7.58(m，2H，ArH)， 7.97(d，J＝7.6Hz，2H，ArH)，8.03(d，J＝8Hz，2H，ArH)
20 0.87(s，3H，CH 3)，1.22(s，3H，CH 3)，2.89(s，3H，N-CH 3)，6.71(d，J＝7.7Hz， 1H，ArH)，6.89(t，1H，ArH)，6.97-7.01(m，1H，ArH)，7.06(d，J＝7.1Hz，1H， ArH)，7.18-7.22(m，1H，ArH)，7.24-7.29(m，1H，ArH)
21 1.44(s，3H，CH 3)，1.98(s，3H，CH 3)，7.29-7.42(m，4H，ArH)，7.47-7.53(m，2H， ArH)，7.65(d，J＝8.5Hz，1H，ArH)，7.72(d，J＝8.6Hz，1H，ArH)， 7.86-7.92(m，4H，ArH)
22 2.18(s，3H，CH 3)，6.96-7.06(m，3H，ArH)，7.19(t，1H，ArH)，7.27-7.32(m，4H， ArH)，7.38(d，J＝8.7Hz，1H，ArH)，7.51(t，1H，ArH)，7.97(d，J＝8.2Hz，1H， ArH)，8.03(d，J＝8.4Hz，1H，ArH)
23 1.33-1.38(m，2H，CH 2)，1.47-1.51(m，2H，CH 2)，1.83-1.88(m，2H，CH 2)， 2.04-2.21(m，3H，CH 2)，2.31-2.37(m，1H，CH 2)，7.28-7.31(m，2H，ArH)， 7.35-7.47(m，3H，ArH)，7.53(d，J＝8.5Hz，1H，ArH)，7.60(d，J＝8.5Hz，1H， ArH)，7.69(d，J＝8.7Hz，1H，ArH)，7.84-7.90(m，4H，ArH)
24 1.23(d，J＝12.1Hz，1H，AdaH)，1.57(d，J＝13.3Hz，1H，AdaH)，1.71(t，2H， AdaH)，1.85(s，2H，AdaH)，1.96(s，2H，AdaH)，2.06(d，J＝20.3Hz，2H， AdaH)，2.22(d，J＝13.29Hz，1H，AdaH)，2.68(s，1H，AdaH)，3.01(d，J＝12.4 Hz，2H，AdaH)，7.26(t，1H，ArH)，7.36-7.49(m，4H，ArH)，7.75(d，J＝8.7Hz， 1H，ArH)，7.81(d，J＝8.2Hz，1H，ArH)，7.87-7.95(m，4H，ArH)，8.12(d，J＝ 8.7Hz，1H，ArH)
25 6.94(d，J＝8.4Hz，1H，ArH)，7.06(s，3H，ArH)，7.19-7.41(m，1H，ArH)，7.49(t， 1H，ArH)，7.54(d，J＝8.4Hz，1H，ArH)，7.72-7.77(m，4H，ArH)，7.89(d，J＝ 8.2Hz，1H，ArH)
26 5.97(s，1H，CH)，6.83-6.85(m，1H，ArH)，7.34-7.56(m，10H，ArH)， 7.74-7.80(m，3H，ArH)，7.89-7.94(m，3H，ArH)
27 1.69(s，3H，CH 3)，4.27-4.58(m，9H，FcH)，7.03(d，J＝6.8Hz，1H，ArH)， 7.25-7.42(m，5H，ArH)，7.66-7.72(m，3H，ArH)，7.81(d，J＝7.2Hz，1H，ArH)， 7.91(d，J＝7.3Hz，2H，ArH)
28 4.38(s，8H，FcH)，4.50(s，1H，FcH)，5.61(s，1H，CH)，7.09(d，J＝8.4Hz，1H， ArH)，7.28-7.48(m，4H，ArH)，7.54(d，J＝8.7Hz，1H，ArH)，7.73-7.77(m，3H， ArH)，7.86(d，J＝8.1Hz，1H，ArH)，7.92-7.95(m，2H，ArH)
29 6.53(d，J＝7.7Hz，1H，ArH)，6.71(t，1H，ArH)，6.83(d，J＝8.42Hz，1H，ArH)， 7.25(t，1H，ArH)，7.33-7.56(m，8H，ArH)，7.66-7.69(m，2H，ArH)， 7.78-7.81(m，2H，ArH)，7.87(t，3H，ArH)，7.95(d，J＝8.1Hz，1H，ArH)
30 6.29(d，J＝9.7Hz，1H，CH＝CH)，6.53(d，J＝8.1Hz，1H，CH＝CH)， 7.00-7.03(m，1H，ArH)，7.10-7.13(m，1H，ArH)，7.18(d，J＝9.7Hz，1H，ArH)， 7.29-7.39(m，3H，ArH)，7.43-7.46(m，1H，ArH)，7.54-7.58(m，1H，ArH) 7.66(d，J＝8.4Hz，1H，ArH)，7.83-8.00(m，7H，ArH)
31 6.45(d，J＝9.9Hz，1H，CH＝CH)，6.75(d，J＝8.9Hz，1H，CH＝CH)，7.21(d，J＝ 8.6Hz，1H，ArH)，7.38-7.48(m，4H，ArH)，7.56-7.64(m，3H，ArH)，7.73(d，J＝ 8.4Hz，1H，ArH)，7.79(d，J＝8.1Hz，1H，ArH)，7.84(d，J＝8.7Hz，1H，ArH)， 7.88-8.02(m，6H，ArH)，8.22(d，J＝8.7Hz，1H，ArH)
32 6.55-6.58(m，1H，ArH)，7.12-7.24(m，3H，ArH)，7.34-7.45(m，5H，ArH)， 7.56-7.62(m，2H，ArH)，7.79-8.08(m，9H，ArH)
33 0.95(s，3H，CH 3)，1.12(s，3H，CH 3)，2.82(s，3H，N-CH 3)，6.71(d，J＝7.5Hz， 1H，ArH)，6.87(t，1H，ArH)，7.01(d，J＝7.1Hz，1H，ArH)，7.26-7.43(m，5H， ArH)，7.54(t，1H，ArH)，7.61(d，J＝8.3Hz，1H，ArH)，7.67(d，J＝8.2Hz，1H， ArH)，7.75(d，J＝8.6Hz，1H，ArH)，7.81(d，J＝8.7Hz，1H，ArH)，7.88(t，2H， ArH)，7.94(d，J＝8.2Hz，1H，ArH)
Table 2 compound 1-33's 13C NMR data
Comp. 13C NMR(400MHz，in CDCl 3，ppm)(δ)
1 27.9，77.8，118.3，121.8，122.5，122.6，123.2，123.5，128.0，128.3，128.9，129.7， 139.8，153.0
2 21.6，25.4，34.6，77.6，118.0，121.5，122.3，122.8，122.9，123.1，127.5，127.9， 129.0，129.2，139.9，152.8
3 23.0，29.9，39.5，82.0，118.4，121.7，122.4，123.0，123.1，123.5，127.7，128.1， 128.8，129.6，141.7，152.7
4 24.8，27.9，32.7，36.3，47.1，78.3，118.3，121.7，122.9，123.2，123.8，124.9，127.4， 127.8，129.7，130.0，139.2，153.2
5 26.9，27.2，33.9，34.4，35.0，38.1，80.9，118.2，121.4，122.2，123.7，125.4，125.5， 126.9，127.4，129.3，130.6，137.7，151.5
6 28.7，81.3，118.5，122.0，122.7，123.0，123.2，125.8，126.8，127.6，127.7，128.1， 128.4，129.7，137.7，145.1，153.2
7 86.9，118.9，122.2，122.6，123.2，127.3，128.0，128.6，129.2，129.8，130.4，132.7， 137.4，143.9，153.2
8 79.9，118.2，122.4，123.0，123.4，126.5，127.9，128.4，128.7，129.9，130.3，134.2， 139.8，153.9
9 28.5，55.4，81.0，113.4，118.4，121.9，122.6，123.1，125.7，127.7，128.0，128.3， 129.6，129.7，137.2，138.1，153.1，158.9
10 72.8，110.5，118.2，122.5，122.6，123.2，126.2，128.0，129.1，129.9，130.1，131.5， 143.4，152.8，153.0
11 82.7，118.7，122.5，122.6，122.8，123.2，126.3，126.9，127.2，127.8，128.0，128.4， 128.8，129.1，129.8，130.0，132.1，133.8，135.8，136.3，147.2，152.6
12 26.5，79.6，108.9，111.5，118.2，119.3，122.0，122.5，122.7，123.2，124.9，128.1， 128.4，129.5，129.8，132.1，136.9，142.3，152.3，153.0
13 29.9，40.0，90.7，118.6，122.1，122.3，123.1，123.2，125.2，125.6，127.3，128.0， 128.3，129.5，129.7，137.7，144.2，145.2，153.4
14 27.2，66.5，67.6，68.6，68.9，69.5，78.9，95.0，118.2，121.8，121.9，122.6，123.0， 125.2，127.9，128.0，128.7，129.7，139.2，153.1
15 66.9，67.9，68.8，68.9，69.3，76.5，88.4，118.0，122.1，122.2，123.0，123.2，125.9， 127.7，128.5，129.6，129.8，134.3，153.8
16 87.5，118.8，120.4，122.5，123.1，125.1，125.4，128.3，128.5，128.8，129.8，129.9， 135.5，139.9，147.5，154.0
17 97.7，116.9，118.5，119.8，121.2，121.5，122.1，122.2，122.7，123.1，127.3，128.2， 128.4，129.0，130.0，130.2，132.3，150.4，150.6
18 97.8，112.7，118.3，118.5，120.0，121.2，121.5，122.2，122.7，123.0，124.1，127.2， 127.5，128.1，128.8，129.2，129.8，130.0，130.5，132.3，148.6，150.4
19 100.9，118.4，121.0，122.0，122.8，123.0，127.8，128.6，129.9，130.1，131.8，133.7， 150.4
20 22.8，28.4，29.9，53.2，107.1，117.4，119.3，120.9，121.0，121.9，122.2，122.6， 127.5，127.9，128.4，128.6，129.3，130.1，131.8，136.7，149.4，155.0
21 25.3，27.6，79.7，118.0，119.7，121.2，123.8，125.3，125.4，125.7，127.0，128.1， 128.2，128.4，128.5，129.3，129.5，130.1，130.5，130.8，133.7，141.4，153.8
22 30.1，83.4，118.7，119.5，123.3，123.7，125.2，125.4，126.0，126.4，127.0，127.2， 127.5，127.9，128.1，128.2，128.3，129.4，130.0，130.2，130.7，134.0，139.1，144.4， 154.2
23 22.1，25.8，32.5，35.0，80.1，118.5，119.6，120.9，123.7，125.1，125.3，125.6， 126.0，127.0，128.1，128.4，128.5，129.4，130.0，130.5，130.8，133.6，141.7，153.1
24 27.2，27.6，32.2，33.8，33.9，35.2，36.2，37.9，383.，84.4，119.8，120.6，123.2， 123.8，125.1，125.3，125.7，127.0，127.3，128.1，128.2，128.5，129.6，129.9，130.1， 130.8，133.8，140.0，152.2
25 89.2，118.6，119.7，123.7，125.2，125.4，125.7，126.1，127.0，127.3，127.7，128.0， 128.1，128.3，128.4，129.0，129.4，130.2，130.5，134.0，139.6，141.8，145.0，153.6
26 83.2，118.5，123.4，124.2，125.6，125.7，126.0，127.2，127.5，127.9，128.0，128.6， 128.9，129.0，130.5，130.6，130.9，134.3，137.4，138.6，155.7
27 22.8，67.7，68.0，69.5，70.0，81.3，94.7，117.8，120.0，123.2，123.8，125.0，125.1， 125.4，125.6，127.1，127.8，128.1，128.3，128.5，128.8，130.3，130.5，130.7，133.7， 141.6，153.2
28 66.7，68.1，69.2，69.6，69.9，79.2，86.2，118.2，118.7，119.6，122.9，124.1，125.4， 125.8，126.8，127.2，127.8，128.0，128.2，128.5，128.8，130.1，130.5，131.0，134.2， 137.5，156.2
29 89.1，119.2，120.1，120.2，120.6，122.8，124.2，124.9，125.5，125.8，126.1，126.6， 127.1，127.6，128.1，128.3，128.4，128.8，129.5，130.0，130.3，130.4，130.7，131.0， 134.4，138.8，139.5，141.5，145.9，146.9，155.2
30 98.5，116.9，119.4，120.1，121.5，122.2，123.6，124.2，125.4，126.3，126.4，126.7， 127.0，127.1，127.3，127.5，128.1，128.4，128.6，129.0，129.1，130.2，130.6，130.9， 133.5，134.5，150.2，150.4
31 98.6，113.0，117.0，118.2，119.4，119.7，120.1，121.5，123.7，124.2，124.4，124.7， 125.5，125.7，126.7，127.2，127.5，128.4，128.6，128.8，129.1，129.9，130.6，130.7， 130.9，133.4，134.5，148.5，150.1
32 101.4，1116.9，118.3，118.6，119.3，121.0，122.0，122.9，123.0，123.3，124.2， 124.3，125.0，125.4，125.5，125.7，126.8，127.5，127.7，128.3，128.7，128.8，129.1， 129.9，130.1，130.7，131.1，131.4，133.2，134.4，134.9，150.2
33 23.9，28.6，30.1，51.6，106.5，109.5，116.8，119.1，119.4，121.8，123.8，125.0， 125.2，125.5，126.3，126.8，127.8，128.0，128.3，128.5，128.9，129.2，130.1，130.6， 130.8，132.8，134.4，136.6，149.2，154.7
Molecular formula, productive rate and the ultimate analysis of table 3 compound 1-33
12 C 20H 16O 2 72 83.32(83.31) 5.66(5.59) Do not have
13 C 21H 16O 55 88.72(88.70) 5.76(5.67) Do not have
14 C 24H 20FeO 57 75.40(75.81) 5.03(5.30) Do not have
15 C 23H 18FeO 68 75.12(75.43) 4.67(4.95) Do not have
16 C 25H 16O 68 90.47(90.33) 4.90(4.85) Do not have
17 C 21H 14O 2 66 84.59(84.54) 4.89(4.73) Do not have
18 C 25H 16O 2 67 86.11(86.19) 4.73(4.63) Do not have
19 C 25H 16O 2 76 86.28(86.19) 4.44(4.63) Do not have
20 C 23H 21NO 78 84.17(84.37) 6.49(6.46) 3.97(4.28)
21 C 23H 18O 72 88.89(89.00) 5.60(5.85) Do not have
22 C 28H 20O 81 90.28(90.29) 5.44(5.41) Do not have
23 C 26H 22O 79 89.00(89.11) 6.29(6.33) Do not have
24 C 30H 26O 83 89.85(89.51) 6.80(6.51) Do not have
25 C 33H 22O 76 90.88(91.21) 4.95(5.10) Do not have
26 C 27H 18O 78 90.42(90.47) 5.40(5.06) Do not have
27 C 32H 24FeO 58 79.64(80.01) 4.55(5.04) Do not have
28 C 31H 22FeO 62 79.72(79.84) 4.40(4.75) Do not have
29 C 33H 20O 86 91.89(91.64) 4.60(4.66) Do not have
30 C 29H 18O 2 67 87.47(87.42) 4.11(4.55) Do not have
31 C 33H 20O 2 63 88.63(88.37) 4.77(4.49) Do not have
32 C 33H 20O 2 61 88.22(88.37) 4.53(4.49) Do not have
33 C 33H 25NO 83 86.89(87.09) 5.74(5.89) 3.21(3.28)
Fusing point and the mass-spectrometric data of table 3 compound 1-33
6 160-161 272(22，[M] +)，257(100，[M-CH 3] +)
7 130-131 334(16，[M] +)，257(100，[M-C 6H 5] +)
8 84-85 258(30，[M] +)，257(14，[M-H] +)，181(100，[M-C 6H 5] +)
9 76-77 302(22，[M] +)，287(100，[M-CH 3] +)
10 65-66 248(100，[M] +)，247(81，[M-H] +)，181(41，[M-C 4H 3O] +)
11 199-200 366(100，[M] +)，283(19，[M-C 4H 3S] +)
12 110-111 288(23，[M] +)，273(100，[M-CH 3] +)
13 92-93 284(100，[M] +)
14 116-117 380(90，[M] +)，365(100，[M-CH 3] +)，195(25，[M-C 10H 9Fe] +)
15 147-148 366(100，[M] +)，365(31，[M-H] +)，181(14，[M-C 10H 9Fe] +)
16 302-303 332(100，[M] +)
17 158-159 298(100，[M] +)
18 222-223 348(100，[M] +)
19 212-213 348(93，[M] +)，180(100)
20 234-235 327(65，[M] +)，312(45，[M-CH 3] +)，158(100)
21 146-147 310(34，[M] +)，295(100，[M-CH 3] +)
22 196-197 372(83，[M] +)，357(100，[M-CH 3] +)，295(58，[M-C 6H 5] +)
23 138-139 350(93，[M] +)，307(100)
24 247-248 402(87，[M] +)，281(100)
25 308-309 434(69，[M] +)，357(100，[M-C 6H 5] +)
26 213-214 358(96，[M] +)，357(29，[M-H] +)，281(74，[M-C 6H 5] +)，80(100)
27 178-179 decomposes 480(100，[M] +)，465(8，[M-CH 3] +)，295(5，[M-C 10H 9Fe] +)
28 200-201 466(62，[M] +)，465(5，[M-H] +)，281(4，[M-C 10H 9Fe] +)，121(100)
29 278-279 432(100，[M] +)
30 231-232 398(53，[M] +)，381(100)
31 295-296 448(63，[M] +)，431(100)
32 220-221 448(39，[M] +)，321(100)
33 196-197 427(22，[M] +)，412(5，[M-CH 3] +)，158(100)

Claims (4)

1, a kind of dibenzopyrans and dibenzo spiro-pyrans compounds is characterized in that it is that general formula is the compound of (I):
Figure A2006100140490002C1
R wherein 1, R 2: hydrogen atom, contain 1 to 20 carbon aliphatics substituting group, aromatic substituents, contain the aliphatics substituting group or the aromatic substituents of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom; R 1, R 2Can Cheng Huan, be aliphatics substituting group, the aromatic substituents that contains 1 to 20 carbon, aliphatics substituting group or the aromatic substituents that contains 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom; R 1, R 2Can be identical, also can be different.
2, a kind of dinaphthopyran and dinaphtho spiro-pyrans compounds is characterized in that it is that general formula is the compound of (II):
R wherein 1, R 2: hydrogen atom, contain 1 to 20 carbon aliphatics substituting group, aromatic substituents, contain the aliphatics substituting group or the aromatic substituents of 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom; R 1, R 2Can Cheng Huan, be aliphatics substituting group, the aromatic substituents that contains 1 to 20 carbon, aliphatics substituting group or the aromatic substituents that contains 1 to 20 carbon of aerobic, nitrogen, sulfur heteroatom; R 1, R 2Can be identical, also can be different.
3, the preparation method of dibenzopyrans as claimed in claim 1 or 2 and dibenzo spiro-pyrans compounds, dinaphthopyran and dinaphtho spiro-pyrans compounds is: by diphenylene-oxide or dinaphtho furans and lithium by 1: the 2-2.4 molar ratio reaction, open loop, react with aldehyde, ketone, ester or acid amides at-70 ℃ to-80 ℃ then, the mol ratio of diphenylene-oxide or dinaphtho furans and aldehyde, ketone, ester or acid amides is 1: 0.7-1, dehydration closed-loop forms corresponding dibenzo, dinaphthopyran and dibenzo, dinaphtho spiro-pyrans compounds again.
4, dibenzopyrans as claimed in claim 1 or 2 and dibenzo spiro-pyrans compounds, dinaphthopyran p and the application of dinaphtho spiro-pyrans compounds on medicine and photochromic material.
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