CN102336779A - Dihydronaphtho or dihydroanthra-1,3-oxazine derivatives and synthesis method thereof - Google Patents
Dihydronaphtho or dihydroanthra-1,3-oxazine derivatives and synthesis method thereof Download PDFInfo
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Abstract
The invention relates to dihydronaphtho or dihydroanthra-1,3-oxazine derivatives and a synthesis method thereof. The compounds have the structure shown in the specifications, wherein R refers to 4-OCH3C6H4, 4-CH3C6H4, C6H5, 4-ClC6H4, alpha-C10H7, n-C8H17 and n-C3H7. Oxy-disilicon naphthol or oxy-disilicon anthranol, formaldehyde and primary amine are subjected to Mannich-condensation under mild conditions, and the yield is high. Therefore, the method is an effective way for constructing a dihydronaphtho-1,3-oxazine or dihydroanthra-1,3-oxazine framework, and enriches methods for synthesizing organic heterocyclic compounds.
Description
Technical field
The present invention relates to a kind of dihydro-naphtho or dihydro anthra-1,3-oxazine verivate and compound method thereof.
Background technology
Heteroaromatic compound is a kind of important and common basic skeleton structure in a lot of pharmaceutical intermediates, natural product and the organic photoelectrical material; Thereby; The synthetic of heteroaromatic compound is that modern methodology of organic synthesis is learned one of focus of being paid close attention to, and explore new effective way is the purpose that chemist is seek assiduously always.
3,4-dihydrobenzo or naphtho--1,3-oxazine analog derivative has wide biological activity, and example has antitumor, and powerful pharmacologically active effects such as antibiotic and anti-HIV can be used as sterilant, antiviral agent and medical antineoplastic agent etc.The while phendioxin; 3-oxazine compounds still prepares the important intermediate of one type of novel phenolic resins; Have excellent mechanical property, thermotolerance, electrical insulating property, flame retardant resistance and favorable mechanical property by two hydrogen benzoxazines as the Polybenzoxazine resin that ring-opening polymerization polymerization generation takes place monomer under heating or catalytic effect; Be one type of dark tool development potentiality, the high-performance polymer material that industrial prospect is fine causes that at home and abroad people pay close attention to widely.Therefore, for dihydrobenzo or naphtho--1, the study on the synthesis of 3-oxazine verivate is significant.See also following reference:
(1)?(a)?Kuehne,?M.?E.;?Konopke,?E.?A.
?J?Med?Chem 1962,?
5,?257.?(b)?Kuehne,?M.?E.;?Konopke,?E.?A.;?Lamberd,?B.?F.?
J?Med?Chem 1962,?
5,?281.?(c)?Chylinska,?J.?B.;?Urbanski,?T.?
J?Med?Chem? 1963,?
6,?484;?(d)?Hsu,?L.?Y.;?Lin,?C.?H.
?Heterocycles? 1996,?
43,?2687.?(d)?Wang,?S.;?Li,?Y.?Y.;?Liu,?Y.?H.;?Lu,?A.?J.;?You,?Q.?D.?
Bioorg.?Med.?Chem.?Lett.? 2008,?
18,?4095。
(2)?Chylinska,?J.?B.;?Janowiec,?M.;?Urbanski,?T.?
Br?J?Pharmacol 1971,?
43,?649。
(3)?(a)?Pedersen,?O.?S.;?Pedersen,?E.?B.?
Synthesis 2000,?479.?(b)?Cocuzza,?A.?J.;?Chidester,?D.?R.;?Cordova,?B.?C.;?Jeffrey,?S.;?Parsons,?R.?L.;?Bacheler,?L.?T.;?Erickson-Viitanen,?S.;?Trainor,?G.?L.;?Ko,?S.?S.?
Bioorg.?Med.?Chem.?Lett.?
2001,?
11,?1177。
Summary of the invention:
One of the object of the invention is to provide one type of new dihydro-naphtho or dihydro anthra-1,3-oxazine verivate.
Two of the object of the invention is to provide the preparation method of this verivate.
For achieving the above object, reaction mechanism of the present invention is: benzo two (oxygen two silicon are luxuriant) (
1) or oxygen two silica-based naphthalenes (
8) react with iodobenzene diacetate salt, trifluoromethanesulfonic acid, generation phenyl [adjacent (the silica-based oxygen two silica-based fused phenyls of hydroxyl dimethyl-)] three fluosulfonic acid iodide (
2) or phenyl [adjacent (the hydroxyl dimethyl-is silica-based) naphthyl] three fluosulfonic acid iodide (
9), adding Diisopropylamine successively, furans cesium fluoride (CsF) generates benzyne intermediate earlier
3Or naphthalyne midbody
10, with furans the Diels-Alder reaction takes place immediately, generate oxygen two silica-based oxa-benzo bicyclic alkenes
4Or oxa-naphtho-bicyclic alkene
11The product of gained is dissolved in the THF and obtains oxygen two silicon naphthols with hydrochloric acid generation ring-opening reaction
5Or anthrol
12Oxygen two silica-based naphthols
5Water-soluble/methyl alcohol or anthrol
12Be dissolved in YLENE and formaldehyde and primary amine
6a-gThe Mannich-condensation reaction takes place generate two hydrogen-oxygens, two silica-based naphtho-s-1,3-oxazine verivate
7a-gOr dihydro anthra-1,3-oxazine verivate
13a-f
According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:
A kind of dihydro-naphtho or dihydro anthra-1,3-oxazine verivate is characterized in that, this compound has following structure:
（1）
（2）
Wherein, R is: OCH
3C
6H
4, CH
3C
6H
4, C
6H
5, ClC
6H
4, α-C
10H
7,
n-C
8H
17,
n-C
3H
7
A kind of above-mentioned dihydro-naphtho or dihydro anthra-1 of preparing, the method for 3-oxazine verivate is characterized in that this method has following steps:
A. at inert atmosphere, under the ice-water bath condition, trifluoromethanesulfonic acid and iodobenzene diacetate salt are joined in the methylene dichloride, ice-water bath reaction 0.5～1 hour, room temperature reaction is 2～3 hours afterwards, obtains reaction mixture;
B. under the ice-water bath condition, step a gained reaction soln is joined in the dichloromethane solution of benzo two (oxygen two silicon are luxuriant) or oxygen two silica-based naphthalenes, reacted 0.5～1 hour, room temperature reaction is 3～4 hours afterwards; Under the ice-water bath condition, add Diisopropylamine, furans, cesium fluoride more successively, room temperature reaction 5～6 hours separates and purifies, and obtains oxygen two silica-based oxa-benzo bicyclic alkenes or oxa-naphtho-bicyclic alkene; The structural formula of described oxygen two silica-based oxa-benzo bicyclic alkenes is:
The structural formula of described oxa-naphtho-bicyclic alkene is:
The structural formula of described iodobenzene diacetate salt is: PhI (OAc)
2The structural formula of described benzo two (oxygen two silicon are luxuriant) is:
The structural formula of described oxygen two silica-based naphthalenes is:
The structural formula of described furans is:
The mol ratio of described iodobenzene diacetate salt, trifluoromethanesulfonic acid, benzo two (oxygen two silicon are luxuriant) or oxygen two silica-based naphthalenes, Diisopropylamine, furans and cesium fluoride is: 1.5～2.5:2.0～3.0:1.0～2.0:2.0～3.0:10～12:2.0～3.0;
C. step b gained oxygen two silica-based oxa-benzo bicyclic alkenes or oxa-naphtho-bicyclic alkene and 36% hydrochloric acid are joined in the THF 70～85
oC reaction 3～4 hours separates and purifies, and obtaining is oxygen two silica-based naphthols or oxygen two silica-based anthrols; The structural formula of described oxygen two silica-based naphthols is:
The structural formula of described anthrol is:
The mol ratio of described oxygen two silica-based oxa-benzo bicyclic alkenes or oxa-naphtho-bicyclic alkene, 36% hydrochloric acid is: 1.0～2.0:4.0～5.0;
D. dissolve in step c gained oxygen two silica-based naphthols in water/methyl alcohol or oxygen two silica-based anthrols dissolve in the YLENE; Add formaldehyde, primary amine under the room temperature condition successively; Reacted 3～4 hours, and purified, obtain two hydrogen-oxygens, two silica-based naphtho-s-1 through separating; 3-oxazine verivate or dihydro anthra-1,3-oxazine verivate; The structural formula of described primary amine is:
, wherein, R is: OCH
3C
6H
4, CH
3C
6H
4, C
6H
5, ClC
6H
4, α-C
10H
7,
n-C
8H
17,
n-C
3H
7The mol ratio of described oxygen two silica-based naphthols or oxygen two silica-based anthrols, formaldehyde, primary amine is: 1.0～2.0:3.0～4.0:1.5～2.5.
Phendioxin; 3-oxazine compounds is the important intermediate of one type of novel phenolic resins of preparation; The Polybenzoxazine resin that is generated as the monomer ring-opening polymerization by Er hydrogen benzoxazine has excellent mechanical property, thermotolerance, electrical insulating property, flame retardant resistance and favorable mechanical property, sees also following reference:
1. Tang Zi is imperial, Cui Meiyan, Chen Weiwen, Xia Zanwen, Liu Hanwen
Fine-chemical intermediate 2011,
2, 28..
2. thank pretty, Bao Chunlei, symbol is new
The tropical agriculture science 2004,
24. 59. (b) Chernykh, A.; Agag, T.; Ishida, H.
Macromolecules 2009,
42, 5121..
3. Kudoh,?R.;?Sudo,?A.;?Endo,?T.?
Macromolecules 2010,?
43,?1185.
Therefore be one type of dark tool development potentiality, the high-performance polymer material that industrial prospect is fine.For dihydrobenzo or naphtho--1, the study on the synthesis of 3-oxazine verivate is significant.
The inventive method is a raw material with benzo two (oxygen two silicon are luxuriant) or oxygen two silica-based naphthalenes, prepares oxygen two silica-based naphthols or anthrols through cycloaddition reaction and ring-opening reaction, further studies oxygen two silica-based naphthols or anthrol and formaldehyde and primary amine the Mannich-condensation reaction takes place; Synthesizing dihydro oxygen two silica-based naphtho-s-1,3-oxazine verivate or dihydro anthra-1,3-oxazine verivate; It is simple to have reaction conditions; Advantages such as speed is fast at present, are utilized Mannich-condensation reaction research dihydro anthra-1; The synthetic of 3-oxazine verivate also do not appear in the newspapers, and has certain researching value.
Analyze theoretically, such reaction is to utilize multi-component Mannich-condensation reaction, and oxygen two silica-based naphthols or anthrol and formaldehyde and primary amine react under mild conditions, and productive rate is higher.Therefore, present method is to make up dihydro-naphtho-1,3-oxazine or dihydro anthra-1, and a kind of valid approach of 3-oxazine skeleton has been enriched the compound method of organic heterocyclic molecule.
Embodiment:
The concrete steps of the inventive method are:
A. at inert atmosphere, under the ice-water bath condition, trifluoromethanesulfonic acid and iodobenzene diacetate salt are joined in the methylene dichloride, ice-water bath reaction 0.5～1 hour, room temperature reaction is 2～3 hours afterwards, obtains reaction mixture;
B. under the ice-water bath condition, step a gained reaction soln is joined in the dichloromethane solution of benzo two (oxygen two silicon are luxuriant) or oxygen two silica-based naphthalenes, reacted 0.5～1 hour, room temperature reaction is 3～4 hours afterwards; Under the ice-water bath condition, add Diisopropylamine, furans, cesium fluoride more successively, room temperature reaction 5～6 hours separates and purifies, and obtains oxygen two silica-based oxa-benzo bicyclic alkenes or oxa-naphtho-bicyclic alkene;
C. step b gained oxygen two silica-based oxa-benzo bicyclic alkenes or oxa-naphtho-bicyclic alkene and 36% hydrochloric acid are joined in the THF 70～85
oC reaction 3～4 hours separates and purifies, and obtaining is oxygen two silica-based naphthols or oxygen two silica-based anthrols;
D. dissolve in step c gained oxygen two silica-based naphthols in water/methyl alcohol or oxygen two silica-based anthrols dissolve in the YLENE; Add formaldehyde, primary amine under the room temperature condition successively; Reacted 3～4 hours, and purified, obtain two hydrogen-oxygens, two silica-based naphtho-s-1 through separating; 3-oxazine verivate or dihydro anthra-1,3-oxazine verivate.
Embodiment one: 6,7-oxygen two silica-based-1-naphthols (
5, 1.0～2.0 eq), formaldehyde (3.0～4.0 eq), the 4-anisidine (
6a, 1.5～2.5 eq), resultant two hydrogen-oxygens, two silica-based naphtho-s-1,3-oxazine verivate is: 3-(4-p-methoxy-phenyl)-8,9-oxygen two is silica-based-3,4-dihydro-2
H-Naphtho-[2,1-
e]-1, the 3-oxazine (
7a), yield 90%, the structure of this compound is:
Molecular formula: C
23H
27NO
2Si
3
Chinese named: 3-(4-p-methoxy-phenyl)-8,9-oxygen two is silica-based-3,4-dihydro-2
H-Naphtho-[2,1-
e]-1, the 3-oxazine
English name: 3-(4-methoxyphenyl)-3,4-dihydro-2
H-8, and 9-oxadisilole fused naphtho [2,1-
e]-1,3-oxazine
Molecular weight: 421.64
Outward appearance: white powder
Proton nmr spectra (500 MHz, CDCl
3): δ 0.43 (s, 6H), 0.44 (s, 6H), 3.74 (s, 3H), 4.67 (s, 2H), 5.48 (s, 2H), 6.80 (d,
J=8.5 Hz, 2H), 7.12-7.15 (m, 3H), 7.42 (d,
J=8.5 Hz, 1H), 8.00 (s, 1H), 8.39 (s, 1H) ppm.
Carbon-13 nmr spectra (125 MHz, CDCl
3): δ 1.3,1.4, and 51.4,55.6,81.6,114.6,115.4,120.7,121.4,124.5,125.2,125.4,131.0,133.6,142.7,143.5,144.0,150.0,155.3 ppm.
Embodiment two: 6,7-oxygen two silica-based-1-naphthols (
5, 1.0～2.0 eq), formaldehyde (3.0～4.0 eq), the 4-monomethylaniline (
6b, 1.5～2.5 eq), resultant two hydrogen-oxygens, two silica-based naphtho-s-1,3-oxazine verivate is: 3-(4-aminomethyl phenyl)-8,9-oxygen two is silica-based-3,4-dihydro-2
H-Naphtho-[2,1-
e]-1, the 3-oxazine (
7b), yield 82%, the structure of this compound is:
Molecular formula: C
23H
27NO
2Si
2
Chinese named: 3-(4-aminomethyl phenyl)-8,9-oxygen two is silica-based-3,4-dihydro-2
H-Naphtho-[2,1-
e]-1, the 3-oxazine
English name: 3-(4-methylphenyl)-3,4-dihydro-2
H-8, and 9-oxadisilole fused naphtho [2,1-
e]-1,3-oxazine
Molecular weight: 405.16
Outward appearance: white powder
Proton nmr spectra (500 MHz, CDCl
3): δ 0.45 (s, 6H), 0.46 (s, 6H), 2.28 (s, 3H), 4.72 (s, 2H), 5.55 (s, 2H), 7.06 (d,
J=9.0 Hz, 2H), 7.10 (d,
J=9.0 Hz, 2H), 7.16 (d, J=8.5Hz, 1H), 7.43 (d,
J=8.5 Hz, 1H), 7.98 (s, 1H), 8.38 (s, 1H) ppm.
Carbon-13 nmr spectra (125 MHz, CDCl
3): δ 1.3,1.4, and 20.7,50.8,80.8,115.4,119.2,120.7,124.5,125.2,125.4,129.9,130.9,131.5,133.6,143.4,144.0,146.5,150.0 ppm.
Embodiment three: 6,7-oxygen two silica-based-1-naphthols (
5, 1.0～2.0 eq), formaldehyde (3.0～4.0 eq), aniline (
6c, 1.5～2.5 eq), resultant two hydrogen-oxygens, two silica-based naphtho-s-1,3-oxazine verivate is: 3-phenyl-8,9-oxygen two is silica-based-3,4-dihydro-2
H-Naphtho-[2,1-
e]-1, the 3-oxazine (
7c), yield 84%, the structure of this compound is:
Molecular formula: C
22H
25NO
2Si
2
Chinese named: 3-phenyl-8,9-oxygen two is silica-based-3,4-dihydro-2
H-Naphtho-[2,1-
e]-1, the 3-oxazine
English name: 3-phenyl-3,4-dihydro-2
H-8, and 9-oxadisilole fused naphtho [2,1-
e]-1,3-oxazine
Molecular weight: 395.62
Outward appearance: white powder
Proton nmr spectra (500 MHz, CDCl
3): δ 0.44 (s, 6H), 0.45 (s, 6H), 4.76 (s, 2H), 5.57 (s, 2H), 6.94-6.97 (m, 2H), 7.16-7.19 (m, 3H), 7.27-7.30 (m, 2H), 7.43 (d,
J=8.0 Hz, 1H), 8.00 (s, 1H), 8.40 (s, 1H), ppm.
Carbon-13 nmr spectra (125 MHz, CDCl
3): δ 1.3,1.4,50.6,80.3,115.4,118.8,120.8,121.8,124.4,125.2,125.4,129.4,131.0,133.6,143.5,144.1,148.7,150.0 ppm.
Embodiment four: 6,7-oxygen two silica-based-1-naphthols (
5, 1.0～2.0 eq), formaldehyde (3.0～4.0 eq), the 4-chloroaniline (
6d, 1.5～2.5 eq), resultant two hydrogen-oxygens, two silica-based naphtho-s-1,3-oxazine verivate is: 3-(4-chloro-phenyl-)-8,9-oxygen two is silica-based-3,4-dihydro-2
H-Naphtho-[2,1-
e]-1, the 3-oxazine (
7d), yield 90%, the structure of this compound is:
Molecular formula: C
22H
24ClNO
2Si
2
Chinese named: 3-(4-chloro-phenyl-)-8,9-oxygen two is silica-based-3,4-dihydro-2
H-Naphtho-[2,1-
e]-1, the 3-oxazine
English name: 3-(4-chlorophenyl)-3,4-dihydro-2
H-8, and 9-oxadisilole fused naphtho [2,1-
e]-1,3-oxazine
Molecular weight: 426.06
Outward appearance: white powder
Proton nmr spectra (500 MHz, CDCl
3): δ 0.46 (s, 6H), 0.47 (s, 6H), 4.71 (s, 2H), 5.52 (s, 2H), 7.10 (d,
J=9.0 Hz, 2H), 7.15 (d,
J=8.0 Hz, 1H), 7.22 (d,
J=9.0 Hz, 2H), 7.46 (d,
J=8.0 Hz, 1H), 8.02 (s, 1H), 8.41 (s, 1H) ppm.
Carbon-13 nmr spectra (125 MHz, CDCl
3): δ 1.3,1.4,50.8,80.1,115.0,120.0,121.0,124.4,125.0,125.3,126.8,129.3,131.0,133.6,143.7,144.3,147.4,149.9 ppm.
Embodiment five: 6,7-oxygen two silica-based-1-naphthols
5(1.0～2.0 eq), formaldehyde (3.0～4.0 eq), alpha-naphthylamine
6e(1.5～2.5 eq), resultant two hydrogen-oxygens, two silica-based naphtho-s-1,3-oxazine verivate is: 3-(Alpha-Naphthyl)-8,9-oxygen two is silica-based-3,4-dihydro-2
H-Naphtho-[2,1-
e]-1, the 3-oxazine (
7e), yield 55%, the structure of this compound is:
Molecular formula: C
24H
37NO
2Si
2
Chinese named: 3-(Alpha-Naphthyl)-8,9-oxygen two is silica-based-3,4-dihydro-2
H-Naphtho-[2,1-
e]-1, the 3-oxazine
English name: 3-(α-naphthyl)-3,4-dihydro-2
H-8, and 9-oxadisilole fused naphtho [2,1-
e]-1,3-oxazine.
Molecular weight: 441.16
Outward appearance: yellow powder
Proton nmr spectra (500 MHz, CDCl
3): δ 0.47 (s, 6H), 0.48 (s, 6H), 4.82 (s, 2), 5.62 (s, 2H), 7.11 (d,
J=8.5 Hz, 1H), 7.28-7.31 (m, 1H), 7.43-7.47 (m, 2H), 7.52-7.56 (m, 1H), 7.59-7.62 (m, 2H), 7.87 (d,
J=8.0 Hz, 1H), 8.04 (s, 1H), 8.30 (d,
J=8.5 Hz, 1H), 8.49 (s, 1H) ppm.
Carbon-13 nmr spectra (125 MHz, CDCl
3): δ 1.3 1.4, and 52.3,82.2,115.5,118.0,120.8,123.6,124.6; 124.8,125.3,125.5,126.01,126.04,126.1,128.7,129.1; 131.0,133.7,134.9,143.6,144.1,146.2,149.6 ppm.
Embodiment six: 6,7-oxygen two silica-based-1-naphthols (
5, 1.0～2.0 eq), formaldehyde (3.0～4.0 eq), NSC 9824 (
6f, 1.5～2.5 eq), resultant two hydrogen-oxygens, two silica-based naphtho-s-1,3-oxazine verivate is: 3-octyl group-8,9-oxygen two is silica-based-3,4-dihydro-2
H-Naphtho-[2,1-
e]-1, the 3-oxazine (
7f), yield 76%, the structure of this compound is:
Molecular formula: C
24H
37NO
2Si
2
Chinese named: 3-octyl group-8,9-oxygen two is silica-based-3,4-dihydro-2
H-Naphtho-[2,1-
e]-1, the 3-oxazine
English name: 3-octyl-3,4-dihydro-2
H-8, and 9-oxadisilole fused naphtho [2,1-
e]-1,3-oxazine
Molecular weight: 427.73
Outward appearance: yellow oily
Proton nmr spectra (500 MHz, CDCl
3): δ 0.55 (s, 6H), 0.56 (s, 6H), 1.00 (t,
J=7.0 Hz, 3H), 1.39-1.42 (m, 12H), 2.90 (t,
J=7.0 Hz, 2H), 4.19 (s, 2H), 5.16 (s, 2H), 7.15 (d,
J=8.5 Hz, 2H), 7.47 (d,
J=8.5 Hz, 1H), 8.10 (s, 1H), 8.55 (s, 1H) ppm.
Carbon-13 nmr spectra (125 MHz, CDCl
3): δ 1.3,1.4, and 14.2,22.7,27.4,28.3,29.4,29.6,31.9,50.5,51.8,83.0,114.6,120.2,124.4,125.1,126.0,130.9,133.6,143.2,143.7,149.6 ppm.
Embodiment seven: 6,7-oxygen two silica-based-1-naphthols (
5, 1.0～2.0 eq), formaldehyde (3.0～4.0 eq), propylamine (
6g, 1.5～2.5 eq), resultant two hydrogen-oxygens, two silica-based naphtho-s-1,3-oxazine verivate is: 3-propyl group-8,9-oxygen two is silica-based-3,4-dihydro-2
H-Naphtho-[2,1-
e]-1, the 3-oxazine (
7g), yield 40%, the structure of this compound is:
Molecular formula: C
24H
37NO
2Si
2
Chinese named: 3-propyl group-8,9-oxygen two is silica-based-3,4-dihydro-2
H-Naphtho-[2,1-
e]-1, the 3-oxazine
English name: 3-propyl-3,4-dihydro-2
H-8, and 9-oxadisilole fused naphtho [2,1-
e]-1,3-oxazine
Molecular weight: 357.59
Outward appearance: yellow oily
Proton nmr spectra (500 MHz, CDCl
3): δ 0.50 (s, 6H), 0.51 (s, 6H), 1.00 (t,
J=7.0 Hz, 3H), 1.67-1.71 (m, 2H), 2.83 (t,
J=7.0 Hz, 2H), 4.16 (s, 2H), 5.13 (s, 2H), 7.12 (d, J=8.0Hz, 1H), 7.43 (d,
J=8.0 Hz, 1H), 8.05 (s, 1H), 8.47 (s, 1H) ppm.
Carbon-13 nmr spectra (125 MHz, CDCl
3): δ 1.3,1.4,11.8,21.5,50.5,53.8,83.1,114.7,120.2,124.4,125.1,126.1,131.0,133.6,143.2,143.7,149.6 ppm.
Embodiment eight: the 1-anthrol (
12, 1.0～2.0 eq), formaldehyde (3.0～4.0 eq), the 4-anisidine (
6a, 1.5～2.5 eq), resultant dihydro anthra-1,3-oxazine verivate is: 3-(4-p-methoxy-phenyl)-3,4-dihydro-2
H-anthra [2,1-
e]-1, the 3-oxazine (
13a), yield 65%, the structure of this compound is:
Molecular formula: C
23H
19NO
2
Chinese named: 3-(4-p-methoxy-phenyl)-3,4-dihydro-2
H-anthra [2,1-
e]-1, the 3-oxazine
English name: 3-(4-methoxyphenyl)-3,4-dihydro-2
H-anthra [2,1-
e]-1,3-oxazine
Molecular weight: 341.40
Outward appearance: yellow powder
Proton nmr spectra (500 MHz, CDCl
3): δ 3.73 (s, 3H), 4.67 (s, 2H), 5.53 (s, 2H), 6.81 (d,
J=9.0 2H), 7.08 (d,
J=8.5,1H), 7.16-7.17 (m, 2H), 7.44-7.48 (m, 2H), 7.56 (d,
J=8.5,1H), 7.96-8.03 (m, 2H), 8.33 (s, 1H), 8.72 (s, 1H) ppm.
Carbon-13 nmr spectra (125 MHz, CDCl
3): δ 51.6,55.6, and 81.4,112.8,114.6,120.3,120.7,121.2,124.5,125.4,125.6,126.0,128.1,128.8,131.5,131.7,131.9,142.8,149.5,155.2 ppm.
Embodiment nine: the 1-anthrol (
12, 1.0～2.0 eq), formaldehyde (3.0～4.0 eq), the 4-monomethylaniline (
6b, 1.5～2.5 eq), resultant dihydro anthra-1,3-oxazine verivate is: 3-(4-aminomethyl phenyl)-3,4-dihydro-2
H-anthra [2,1-
e]-1, the 3-oxazine (
13b), yield 43%, the structure of this compound is:
Molecular formula: C
23H
19NO
Chinese named: 3-(4-aminomethyl phenyl)-3,4-dihydro-2
H-anthra [2,1-
e]-1, the 3-oxazine
English name: 3-(4-methylphenyl)-3,4-dihydro-2
H-anthra [2,1-
e]-1,3-oxazine
Molecular weight: 325.40
Outward appearance: yellow powder
Proton nmr spectra (500 MHz, CDCl
3): δ 2.29 (s, 3H), 4.72 (s, 2H), 5.60 (s, 2H), 7.09-7.16 (m, 5H), 7.47-7.49 (m, 2H), 7.57 (d,
J=8.5,1H), 7.98-8.00 (m, 1H), 8.05-8.07 (m, 1H), 8.34 (s, 1H), 8.76 (s, 1H) ppm.
Carbon-13 nmr spectra (125 MHz, CDCl
3): δ 20.7,51.0, and 80.6,112.8,119.0,120.3,120.7,124.4,124.5,125.4,125.6,126.0,128.1,128.8,129.9,131.3,131.5,131.6,131.8,146.6,149.5 ppm.
Embodiment ten: the 1-anthrol (
12, 1.0～2.0 eq), formaldehyde (3.0～4.0 eq), aniline (
6c, 1.5～2.5 eq), resultant dihydro anthra-1,3-oxazine verivate is: 3-phenyl-3,4-dihydro-2
H-anthra [2,1-
e]-1, the 3-oxazine (
13c), yield 62%, the structure of this compound is:
Molecular formula: C
22H
17NO
Chinese named: 3-phenyl-3,4-dihydro-2
H-anthra [2,1-
e]-1, the 3-oxazine
English name: 3-phenyl-3,4-dihydro-2
H-anthra [2,1-
e]-1,3-oxazine
Molecular weight: 311.38
Outward appearance: yellow powder
Proton nmr spectra (500 MHz, CDCl
3): δ 4.75 (s, 2H), 5.62 (s, 2H), 6.96-6.99 (m, 1H), 7.10 (d,
J=8.5 Hz, 1H), 7.23-7.25 (m, 2H), 7.30-7.33 (m, 2H), 7.48-7.50 (m, 2H), 7.57 (d,
J=8.5 Hz, 1H), 7.98-8.00 (m, 1H), 8.05-8.07 (m, 1H), 8.34 (s, 1H), 8.76 (s, 1H) ppm.
Carbon-13 nmr spectra (125 MHz, CDCl
3): δ 50.8,80.0, and 112.8,118.5,120.2,120.8,121.7,124.4,124.5,125.4,125.6,126.0,128.1,128.8,129.4,131.5,131.6,131.9,148.8,149.6 ppm.
Embodiment 11: the 1-anthrol (
12, 1.0～2.0 eq), formaldehyde (3.0～4.0 eq), the 4-chloroaniline (
6d, 1.5～2.5 eq), resultant dihydro anthra-1,3-oxazine verivate is: 3-(4-chloro-phenyl-)-3,4-dihydro-2
H-anthra [2,1-
e]-1, the 3-oxazine (
13d), yield 60%, the structure of this compound is:
Molecular formula: C
22H
16ClNO
Chinese named: 3-(4-chloro-phenyl-)-3,4-dihydro-2
H-anthra [2,1-
e]-1, the 3-oxazine
English name: 3-(4-chlorophenyl)-3,4-dihydro-2
H-anthra [2,1-
e]-1,3-oxazine
Molecular weight: 345.82
Outward appearance: yellow powder
Proton nmr spectra (500 MHz, CDCl
3): δ 4.69 (s, 2H), 5.55 (s, 2H), 7.06-7.14 (m, 3H), 7.21-7.24 (m, 2H), 7.45-7.49 (m, 2H), 7.57 (d,
J=8.5 Hz, 1H), 7.97-8.04 (m, 2H), 8.33 (s, 1H), 8.71 (s, 1H) ppm.
Carbon-13 nmr spectra (125 MHz, CDCl
3): δ 51.0,79.9, and 112.5,119.9,120.2,121.0,124.2,124.4,125.6,125.8,126.1,126.7,128.1,128.8,129.3,131.6,131.6,131.9,147.5,149.5 ppm.
Embodiment 12: the 1-anthrol (
12, 1.0～2.0 eq), formaldehyde (3.0～4.0 eq), alpha-naphthylamine (
6e, 1.5～2.5 eq), resultant dihydro anthra-1,3-oxazine verivate is: 3-Alpha-Naphthyl-3,4-dihydro-2
H-anthra [2,1-
e]-1, the 3-oxazine (
13e), yield 42%, the structure of this compound is:
Molecular formula: C
26H
19NO
Chinese named: 3-(Alpha-Naphthyl)-3,4-dihydro-2
H-anthra [2,1-
e]-1, the 3-oxazine
English name: 3-(α-naphthyl)-3,4-dihydro-2
H-anthra [2,1-
e]-1,3-oxazine
Molecular weight: 361.44
Outward appearance: yellow powder
Proton nmr spectra (500MHz, CDCl
3): δ 4.78 (b, 2H), 5.66 (s, 2H), 7.04 (d,
J=9.0 Hz, 1H), 7.28-7.31 (m, 1H), 7.47-7.62 (m, 7H), 7.87 (d,
J=8.5 Hz, 1H), 7.98-8.07 (m, 2H), 8.31-8.35 (m, 2H), 8.80 (s, 1H) ppm.
Carbon-13 nmr spectra (125 MHz, CDCl
3): δ 52.4,82.2, and 112.9,117.7,120.3,120.8,123.7,124.5; 124.8,125.5,125.7,126.02,126.04,126.1,128.1,128.7; 128.8,129.1,131.6,1317,131.9,134.9,146.3,149.1 ppm.
Embodiment 13: the 1-anthrol (
12, 1.0～2.0 eq), formaldehyde (3.0～4.0 eq), NSC 9824 (
6f, 1.5～2.5 eq), resultant dihydro anthra-1,3-oxazine verivate is: 3-octyl group-3,4-dihydro-2
H-anthra [2,1-
e]-1, the 3-oxazine (
13f), yield 62%, the structure of this compound is:
Molecular formula: C
24H
29NO
Chinese named: 3-octyl group-3,4-dihydro-2
H-anthra [2,1-
e]-1, the 3-oxazine
English name: 3-octyl-3,4-dihydro-2
H-anthra [2,1-
e]-1,3-oxazine
Molecular weight: 347.49
Outward appearance: yellow oily
Proton nmr spectra (500 MHz, CDCl
3): δ 0.92 (t,
J=7.0 Hz, 3H), 1.30-1.35 (m, 12H), 2.86 (t,
J=7.0 Hz, 2H), 4.13 (s, 2H), 5.14 (s, 2H), 7.06 (d,
J=9.0,1H), 7.46-7.48 (m, 2H), 7.55 (d,
J=8.5,1H), 7.98-8.07 (m, 2H), 8.34 (s, 1H), 8.74 (s, 1H) ppm.
Carbon-13 nmr spectra (125 MHz, CDCl
3): δ 14.2,22.8, and 27.4,28.5,29.4,29.7,32.0,50.6; 52.1,83.1,112.1,120.1,120.2,124.3,125.3,125.3; 125.5,126.0,128.1,128.8,131.5,131.7,131.8,149.1 ppm.
Claims (2)
1. dihydro-naphtho or dihydro anthra-1,3-oxazine verivate is characterized in that, this compound has following structure:
（1）
（2）
Wherein, R is: OCH
3C
6H
4, CH
3C
6H
4, C
6H
5, ClC
6H
4, α-C
10H
7,
n-C
8H
17,
n-C
3H
7
2. one kind prepares dihydro-naphtho according to claim 1 or dihydro anthra-1, and the method for 3-oxazine verivate is characterized in that this method has following steps:
A. at inert atmosphere, under the ice-water bath condition, trifluoromethanesulfonic acid and iodobenzene diacetate salt are joined in the methylene dichloride, ice-water bath reaction 0.5～1 hour, room temperature reaction is 2～3 hours afterwards, obtains reaction mixture;
B. under the ice-water bath condition, step a gained reaction soln is joined in the dichloromethane solution of benzo two (oxygen two silicon are luxuriant) or oxygen two silica-based naphthalenes, reacted 0.5～1 hour, room temperature reaction is 3～4 hours afterwards; Under the ice-water bath condition, add Diisopropylamine, furans, cesium fluoride more successively, room temperature reaction 5～6 hours separates and purifies, and obtains oxygen two silica-based oxa-benzo bicyclic alkenes or oxa-naphtho-bicyclic alkene; The structural formula of described oxygen two silica-based oxa-benzo bicyclic alkenes is:
The structural formula of described oxa-naphtho-bicyclic alkene is:
The structural formula of described iodobenzene diacetate salt is: PhI (OAc)
2The structural formula of described benzo two (oxygen two silicon are luxuriant) is:
The structural formula of described oxygen two silica-based naphthalenes is:
The structural formula of described furans is:
The mol ratio of described iodobenzene diacetate salt, trifluoromethanesulfonic acid, benzo two (oxygen two silicon are luxuriant) or oxygen two silica-based naphthalenes, Diisopropylamine, furans and cesium fluoride is: 1.5～2.5:2.0～3.0:1.0～2.0:2.0～3.0:10～12:2.0～3.0;
C. step b gained oxygen two silica-based oxa-benzo bicyclic alkenes or oxa-naphtho-bicyclic alkene and 36% hydrochloric acid are joined in the THF 70～85
oC reaction 3～4 hours separates and purifies, and obtaining is oxygen two silica-based naphthols or oxygen two silica-based anthrols; The structural formula of described oxygen two silica-based naphthols is:
The structural formula of described anthrol is:
The mol ratio of described oxygen two silica-based oxa-benzo bicyclic alkenes or oxa-naphtho-bicyclic alkene, 36% hydrochloric acid is: 1.0～2.0:4.0～5.0;
D. dissolve in step c gained oxygen two silica-based naphthols in water/methyl alcohol or oxygen two silica-based anthrols dissolve in the YLENE; Add formaldehyde, primary amine under the room temperature condition successively; Reacted 3～4 hours, and purified, obtain two hydrogen-oxygens, two silica-based naphtho-s-1 through separating; 3-oxazine verivate or dihydro anthra-1,3-oxazine verivate; The structural formula of described primary amine is:
, wherein, R is: OCH
3C
6H
4, CH
3C
6H
4, C
6H
5, ClC
6H
4, α-C
10H
7,
n-C
8H
17,
n-C
3H
7The mol ratio of described oxygen two silica-based naphthols or oxygen two silica-based anthrols, formaldehyde, primary amine is: 1.0～2.0:3.0～4.0:1.5～2.5.
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| CN104072532A (en) * | 2014-04-14 | 2014-10-01 | 上海大学 | Silicon oxide naphthopyran or anthracene pyran derivative and synthesis method thereof |
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| CN104072532A (en) * | 2014-04-14 | 2014-10-01 | 上海大学 | Silicon oxide naphthopyran or anthracene pyran derivative and synthesis method thereof |
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