CN103319423B - The synthetic method of two aryl-1,5-dioxy-3, the 7-diazo-cyclooc-tane of a kind of 3,7- - Google Patents
The synthetic method of two aryl-1,5-dioxy-3, the 7-diazo-cyclooc-tane of a kind of 3,7- Download PDFInfo
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Abstract
The present invention relates to the synthetic method of two aryl-1,5-dioxy-3, the 7-diazo-cyclooc-tane of a kind of 3,7-, belong to Azacrown ether containing synthesis technical field.Aromatic amine mixes with formalin by this synthetic method, 3 are obtained after reaction, the two aryl-1 of 7-, 5-dioxy-3,7-diazo-cyclooc-tane, this synthetic method is with silicon sulfonic acid for catalyzer, and productive rate and purity are all higher and speed of response is fast, filter the recovery and the generation of no acidic waste liquid that can realize catalyzer by means of only simple after reaction terminates, product purity is higher; Synthetic method provided by the invention is without the need to carrying out heating and pressurizing, and reaction bar is gentle, and without additional energy, cost is lower.<pb pnum="1" />
Description
Technical field
The present invention relates to the synthetic method of two aryl-1,5-dioxy-3, the 7-diazo-cyclooc-tane of a kind of 3,7-, belong to Azacrown ether containing synthesis technical field.
Background technology
Two aryl-1,5-dioxy-3, the 7-diazo-cyclooc-tane of 3,7-is a class eight yuan of Azacrown ether containings, can be used as immunostimulant (Kolar G.F., Schendzielorz M., Ger.Offen.1985, DE3421062, A1,1985-12-12).Because eight yuan of Azacrown ether containings can prevent photofading, Yutaka etc. think that this compounds can be applied to (Yutaka K., Jpn.Kokai Tokyo Koho in the industries such as photography, cloth dyeing and ink manufacture, 1988, JP 63311352, A, 1988-12-20).Thus, for a kind of easy, efficient synthetic method of this compounds exploitation has certain theory significance and using value.
Due to octatomic ring relative to five yuan, six-ring compound or macrocylc compound, ring strain is larger, its synthesis is problem (Zhu Mianxia the most difficult in ring system synthesis, Wang Zhumei, Zhan Hongquan, Jiangxi Normal University's journal (natural science edition), 2007,31 (6): 584-587).The method of general synthesis octatomic ring system mainly contains: (the Li Zhengbang such as D-A reaction and aldol condensation in alkylation in carbonyl coupling, molecule, molecule, Wang Fengpeng, Chen Donglin. the structure [J] of carbocyclic eight-membered ring in natural product synthesis. organic chemistry, 2000,20 (3): 282-292), but these methods are only suitable for synthesis carbocyclic eight-membered ring compound, and therefore the synthesis of eight yuan of heterocycles is a difficult problem always.Up to the present the synthesis of two sections of bibliographical informations, eight yuan of Azacrown ether containings is only had:
(1) 1985 year, Kolar seminar has reported synthesis (the Kolar G.F. of this compounds first, Schendzielorz M., Tetrahedron lett., 1985,26 (8): p.1043-1044), the method is an accidental discovery, four steps need be experienced, have to four products.Except reaction substrate, also need to add three kinds of reagent, and severe reaction conditions, the time long (spending the night), process and aftertreatment are very loaded down with trivial details, and yield only has 18-53%.
Within (2) 2006 years, Kakane jadifard seminar 3-N-methyl-p-nitroaniline and formaldehyde have synthesized 3,7-is two-(3-nitrophenyl)-1,5-dioxy-3,7-phenodiazine cyclooctane (Kakane jadifard A., MahmodiL., Yanr A.and Mohajeri A., J.Heterocyclic Chem., 2006,43 (6): p.1695-1697), yield 84%, but have to this product, and the reaction times reaches 24h.
Summary of the invention
The object of the invention is for overcoming above-mentioned the deficiencies in the prior art part, a kind of 3,7-synthetic method of two aryl-1,5-dioxy-3,7-diazo-cyclooc-tane is provided.Aromatic amine mixes with formalin by the method, obtains two aryl-1,5-dioxy-3, the 7-diazo-cyclooc-tane of 3,7-, synthetic method speed of response provided by the invention is fast, mild condition, technique is simple after reaction, the products collection efficiency obtained and purity higher.
The present invention realizes with following technical scheme: a kind of 3, the two aryl-1 of 7-, the synthetic method of 5-dioxy-3,7-diazo-cyclooc-tane, is characterized in that: this synthetic method comprises: aromatic amine is dissolved in polar solvent, add formalin, two aryl-1, the 5-dioxy-3 of 3,7-is obtained after reaction under silicon sulfonic acid catalyzes, 7-diazo-cyclooc-tane, described aromatic amine is the amino aromatic amine be connected with the carbon on aromatic nucleus.
Described aromatic amine is the arylamine with electron withdrawing group on aromatic ring.
Described aromatic amine is 4-aminobenzonitrile, 4-5-trifluoromethylaniline, 3-N-methyl-p-nitroaniline, 4-N-methyl-p-nitroaniline, 4-aminoacetophenone, PABA, 3,4-DCA, the chloro-4-fluoroaniline of 3-or 5-amino-2-chlorobenzotrifluoride.
Described formalin is 37% formalin.
The mol ratio of described aromatic amine and described formalin is 1:5-6.
Described catalyzer is silicon sulfonic acid.
The temperature of reacting under described silicon sulfonic acid catalyzes is 20 DEG C-30 DEG C.
The time of reacting under described silicon sulfonic acid catalyzes is 5min-15min.
Described polar solvent is ethyl acetate.
Advantage of the present invention is: this synthetic method is with silicon sulfonic acid for catalyzer, and productive rate and purity are all higher and speed of response fast, and filter the recovery and the generation of no acidic waste liquid that can realize catalyzer by means of only simple after reaction terminates, product purity is higher; Synthetic method provided by the invention is without the need to carrying out heating and pressurizing, and reaction bar is gentle, and without additional energy, cost is lower.
Embodiment
The invention provides a kind of 3, the two aryl-1 of 7-, the synthetic method of 5-dioxy-3,7-diazo-cyclooc-tane, comprising: aromatic amine is dissolved in ethyl acetate, add formalin and silicon sulfonic acid, two aryl-1, the 5-dioxy-3 of 3,7-is obtained after reaction, 7-diazo-cyclooc-tane, described aromatic amine is the amino aromatic amine be connected with the carbon on aromatic nucleus.
According to the present invention, described aromatic amine is the amino aromatic amine be connected with the carbon on aromatic nucleus.Described aromatic amine is preferably the arylamine with electron withdrawing group, be more preferably position or contraposition between amino and have the arylamine of electron withdrawing group, most preferably be 4-aminobenzonitrile, 4-5-trifluoromethylaniline, 3-N-methyl-p-nitroaniline, 4-N-methyl-p-nitroaniline, 4-aminoacetophenone, PABA, 3,4-DCA, the chloro-4-fluoroaniline of 3-or 5-amino-2-chlorobenzotrifluoride.The source of the present invention to described aromatic amine is not particularly limited, and preferably buys from the market.
Formaldehyde is the necessary raw material of two aryl-1,5-dioxy-3, the 7-diazo-cyclooc-tanes of synthesis 3,7-, the present invention with 37% formalin for raw material.The source of the present invention to described 37% formalin is not particularly limited, and preferably buys from the market.
In order to make reaction more abundant, the mol ratio of described aromatic amine and described 37% formalin is preferably 1:1-10, is more preferably 1:1-8, most preferably is 1:6.
The present invention preferably carries out stirring well known to those skilled in the art to the mixture of described aromatic amine and described 37% formalin, accelerates its reaction.When described aromatic amine and described 37% formalin react, temperature of reaction is preferably 18 DEG C-50 DEG C, is more preferably 20 DEG C-40 DEG C, most preferably is 22 DEG C-30 DEG C; The time of described reaction is preferably 1min-60min, is more preferably 2min-30min, most preferably is 5min-15min; Reaction solvent is preferably ethanol, acetone, acetonitrile, ionic liquid, water, ethyl acetate and methylene dichloride, is more preferably acetoneand ethyl acetate, most preferably is ethyl acetate.
Be described in detail below in conjunction with the synthetic method of embodiment to provided by the invention 3,7-two aryl-1,5-dioxy-3,7-diazo-cyclooc-tanes.
Embodiment 1,
2mmol(0.23g is added in 50mL round-bottomed flask) p-aminophenyl nitrile and 1.0g37% formalin, after stirred at ambient temperature 5min, filter, solid hot ethanol dissolves, and refilters removing silicon sulfonic acid, filtrate rotary evaporation removing ethanol, obtain 0.22g product, productive rate 71%, purity 99.9%.Described product structure is confirmed through proton nmr spectra, carbon spectrum and high resolution mass spectrum, and spectroscopic data is as follows:
1h NMR (400MHz, DMSO-d
6) δ (ppm) 7.37 (d, J=8.0Hz, ArH, 4H), 6.89 (d, J=8.0Hz, ArH, 4H), 5.70-4.95 (dr, CH
28H);
13c NMR (100MHz, DMSO-d
6) δ 147.7,132.3,119.7,114.6,99.7,81.4; HRMS (ESI, m/z): calcd.for C
18h
16n
4o
2na (M+Na
+) 343.1171, found 343.1195.As can be seen here, described product be 3,7-two-(4-cyano-phenyl)-1,5-dioxy-3,7-diazo-cyclooc-tane, English name is 3,7-Bis-(4-cyanphenyl)-1,5-dioxa-3,7-diazacyclooctane.
Embodiment 2,
2mmol(0.32g is added in 50mL round-bottomed flask) 4-5-trifluoromethylaniline and 1.0g37% formalin, after stirred at ambient temperature 5min, filter, solid hot ethanol dissolves, and refilters removing silicon sulfonic acid, filtrate rotary evaporation removing ethanol, obtain 0.42g product, productive rate 70%, purity 99.9%.Described product structure is confirmed through proton nmr spectra, carbon spectrum and high resolution mass spectrum, and spectroscopic data is as follows:
1h NMR (400MHz, DMSO-d
6) δ (ppm) 7.21 (d, J=8.0Hz, ArH, 4H), 6.91 (d, J=8.0Hz, ArH, 4H), 5.81-4.83 (dr, CH
2, 8H);
13c NMR (100MHz, DMSO-d
6) δ 146.2,130.6,118.5,113.4,98.7,80.2; HRMS (ESI, m/z): calcd.for C
18h
16f
6o
2na (M+Na
+) 429.1014, found 429.0969. as can be seen here, described product is 3,7-is two-(4-trifluoromethyl)-1,5-dioxy-3,7-diazo-cyclooc-tane, English name is: 3,7-Bis-(4-trifluoromethylphenyl)-1,5-dioxa-3,7-diazacyclooctane.
Embodiment 3,
2mmol(0.28g is added in 50mL round-bottomed flask) 3-N-methyl-p-nitroaniline and 1.0g37% formalin, after stirred at ambient temperature 5min, filter, solid hot ethanol dissolves, and refilters removing silicon sulfonic acid, filtrate rotary evaporation removing ethanol, obtain 0.55g product, productive rate 98%, purity 99.9%.Described product structure is confirmed through proton nmr spectra, carbon spectrum and high resolution mass spectrum, and spectroscopic data is as follows:
1h NMR (400MHz, DMSO-d
6) δ (ppm) 7.54 (t, J=2.0Hz, ArH, 2H), 7.30 (dd, J=8.0Hz, ArH, 2H), 7.23 (dd, J=8.0Hz, ArH, 2H), 7.16 (t, J=8.0Hz, ArH, 2H), 5.70-5.00 (dr, CH
2, 8H), 5.23 (s, CH
2, 4H);
13c NMR (100MHz, DMSO-d
6) δ 147.7,145.0,128.9,121.0,112.8,109.0,81.4; HRMS (ESI, m/z): calcd.forC
16h
16n
4o
6na (M+Na
+) 383.0968, found 383.1009. as can be seen here, described product be 3,7-two-(3-nitrophenyl)-1,5-dioxy-3,7-diazo-cyclooc-tane, English name is: 3,7-Bis-(3-nitrophenyl)-1,5-dioxa-3,7-diazacyclooctane.
Embodiment 4,
2mmol(0.28g is added in 50mL round-bottomed flask) 4-N-methyl-p-nitroaniline and 1.0g37% formalin, after stirred at ambient temperature 5min, filter, solid hot ethanol dissolves, and refilters removing silicon sulfonic acid, filtrate rotary evaporation removing ethanol, obtain 0.50g product, productive rate 90%, purity 99.9%.Described product structure is confirmed through proton nmr spectra, carbon spectrum and high resolution mass spectrum, and spectroscopic data is as follows:
1h NMR (400MHz, DMSO-d
6) δ (ppm) 7.83 (4H, d, J=12.0Hz, ArH), 6.94 (4H, d, J=8.0Hz, ArH), 5.64-5.12 (8H, dr, CH
2);
13c NMR (100MHz, DMSO-d
6) δ 145.0,138.5,124.4,114.1,81.5; HRMS (ESI, m/z): calcd.for C
16h
16n
4o
6na (M+Na
+) 383.0968, found 383.0940. as can be seen here, described product be 3,7-two-(4-nitrophenyl)-1,5-dioxy-3,7-diazo-cyclooc-tane, English name is:
3,7-Bis-(4-nitrophenyl)-1,5-dioxa-3,7-diazacyclooctane.
Embodiment 5,
2mmol(0.27g is added in 50mL round-bottomed flask) 4-aminoacetophenone and 1.0g37% formalin, after stirred at ambient temperature 5min, filter, solid hot ethanol dissolves, and refilters removing silicon sulfonic acid, filtrate rotary evaporation removing ethanol, obtain 0.28g product, productive rate 51%, purity 99.9%.Described product structure is confirmed through proton nmr spectra, carbon spectrum and high resolution mass spectrum, and spectroscopic data is as follows:
1h NMR (400MHz, DMSO-d
6) δ (ppm)
1h NMR (400MHz, DMSO) δ 7.59 (d, J=8.6Hz, ArH, 4H), 6.91 (d, J=8.7Hz, ArH, 4H), 5.69-4.99 (dr, CH
2, 8H);
13c NMR (100MHz, DMSO-d
6) δ 195.8,148.5,129.2,127.6,113.5,81.8,26.0; HRMS (ESI, m/z): calcd.for C
20h
22n
2o
4na (M+Na
+) 377.1477, found 377.1468. as can be seen here, described product be 3,7-two-(4-acetylphenyl)-1; 5-dioxy-3,7-diazo-cyclooc-tane, English name is: 3; 7-Bis-(4-acetylphenyl)-1,5-dioxa-3,7-diazacyclooctane
Embodiment 6,
2mmol(0.29g is added in 50mL round-bottomed flask) the chloro-4-fluoroaniline of 3-and 1.0g37% formalin, after stirred at ambient temperature 15min, filter, solid hot ethanol dissolves, and refilters removing silicon sulfonic acid, filtrate rotary evaporation removing ethanol, obtain 0.32g product, productive rate 56%, purity 99.9%.Described product structure is confirmed through proton nmr spectra, carbon spectrum and high resolution mass spectrum, and spectroscopic data is as follows:
1h NMR (400MHz, DMSO-d
6) δ (ppm) 7.01 (t, J=9.1Hz, ArH, 2H), 6.92 (dd, J=6.4,2.9Hz, ArH, 2H), 6.87 – 6.76 (m, ArH, 2H), 5.49-4.92 (dr, CH
2, 8H);
13c NMR (100MHz, DMSO-d
6) δ 151.8,149.4,141.6,118.7,116.3,115.8,115.6,114.9,81.8; HRMS (ESI, m/z): calcd.for C
16h
14cl
2f
2n
2o
2na (M+Na
+) 397.0298, found397.0291. as can be seen here, described product is 3,7-pair-(the chloro-4-fluorophenyl of 3-)-1,5-dioxy-3,7-diazo-cyclooc-tane, English name is: 3,7-Bis-(3-chlor-4-fluorphenyl)-1,5-dioxa-3,7-diazacyclooctane
Embodiment 7,
2mmol(0.39g is added in 50mL round-bottomed flask) 5-amino-2-chlorobenzotrifluoride and 1.0g37% formalin, after stirred at ambient temperature 15min, filter, solid hot ethanol dissolves, refilter removing silicon sulfonic acid, filtrate rotary evaporation removing ethanol, obtains 0.48g product, productive rate 72%, purity 99.9%.Described product structure is confirmed through proton nmr spectra, carbon spectrum and high resolution mass spectrum, and spectroscopic data is as follows:
1h NMR (400MHz, DMSO-d
6) δ (ppm) 7.22 (d, J=8.8Hz, ArH, 2H), 7.07 (s, ArH, 4H), 5.63-4.95 (dr, CH
2, 8H);
13c NMR (100MHz, DMSO-d
6) δ 143.06,130.73,126.27,124.08,121.37,119.36,113.41,81.32; HRMS (ESI, m/z): calcd.for C
16h
14cl
2f
2n
2o
2na (M+Na
+) 497.0234, found 497.0239. as can be seen here, described product is 3,7-pair-(3-trifluoromethyl 4-chloro-phenyl-)-1,5-dioxy-3,7-diazo-cyclooc-tane, English name is: 3,7-Bis-(3-trifluoromethyl-4-chlorphenyl)-1,5-dioxa-3,7-diazacyclooctane.
Embodiment 8,
2mmol(0.32g is added in 50mL round-bottomed flask) 3,4-DCA and 1.0g 37% formalin, after stirred at ambient temperature 15min, filter, solid hot ethanol dissolves, and refilters removing silicon sulfonic acid, filtrate rotary evaporation removing ethanol, obtain 0.42g product, productive rate 70%, purity 99.9%.Described product structure is confirmed through proton nmr spectra, carbon spectrum and high resolution mass spectrum, and spectroscopic data is as follows:
1h NMR (400MHz, DMSO-d
6) δ (ppm) 7.17 (d, J=9.0Hz, ArH, 2H), 6.95 (d, J=2.8Hz, ArH, 2H), 6.80 (dd, J=9.0,2.8Hz, ArH, 2H), 5.52-4.90 (dr, CH
2, 8H);
13c NMR (100MHz, DMSO-d
6) δ 144.1,130.7,129.3,120.1,116.4,115.0,81.5; HRMS (ESI, m/z): calcd.for C
16h
14cl
4n
2o
2na (M+Na
+) 430.9678, found430.9672. as can be seen here, described product is 3,7-two-(3,4-dichlorophenyl)-1,5-dioxy-3,7-diazo-cyclooc-tane, English name is: 3,7-Bis-(3,4-dichlorphenyl)-1,5-dioxa-3,7-diazacyclooctane.
Embodiment 9,
2mmol(0.27g is added in 50mL round-bottomed flask) PABA and 1.0g37% formalin, after stirred at ambient temperature 8min, filter, solid hot ethanol dissolves, and refilters removing silicon sulfonic acid, filtrate rotary evaporation removing ethanol, obtain 0.32g product, productive rate 60%, purity 99.9%.Described product structure is confirmed through proton nmr spectra, carbon spectrum and high resolution mass spectrum, and spectroscopic data is as follows:
1h NMR (400MHz, DMSO-d
6) δ (ppm) 12.22 (s, COOH, 2H), 7.57 (d, J=8.9Hz, ArH, 4H), 6.91 (d, J=8.9Hz, ArH, 4H), 5.55-5.06 (dr, CH
2, 8H);
13c NMR (100MHz, DMSO-d
6) δ 172.4,153.5,135.3,125.7,118.7,87.0; HRMS (ESI, m/z): calcd.forC18H18N2O6Na [M+Na]+381.1063, found 381.1056.As can be seen here, described product be 3,7-two-(4-carboxyl phenyl)-1,5-dioxy-3,7-diazo-cyclooc-tane, English name is: 3,7-Bis-(4-carboxylphenyl)-1,5-dioxa-3,7-diazacyclooctane.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (3)
1. one kind 3, the two aryl-1 of 7-, the synthetic method of 5-dioxy-3,7-diazo-cyclooc-tane, is characterized in that: this synthetic method comprises: aromatic amine is dissolved in polar solvent, add formalin, two aryl-1, the 5-dioxy-3 of 3,7-is obtained after reaction under silicon sulfonic acid catalyzes, 7-diazo-cyclooc-tane, described aromatic amine is the amino aromatic amine be connected with the carbon on aromatic nucleus;
Described catalyzer is silicon sulfonic acid;
The temperature of reacting under described silicon sulfonic acid catalyzes is 20 DEG C-30 DEG C;
The time of reacting under described silicon sulfonic acid catalyzes is 5min-15min;
Described formalin is 37% formalin;
The mol ratio of described aromatic amine and formalin is 1:5-6;
Described aromatic amine is the arylamine with electron withdrawing group on aromatic ring.
2. according to claim 13, the two aryl-1 of 7-, 5-dioxy-3, the synthetic method of 7-diazo-cyclooc-tane, it is characterized in that: described aromatic amine is 4-aminobenzonitrile, 4-5-trifluoromethylaniline, 3-N-methyl-p-nitroaniline, 4-N-methyl-p-nitroaniline, 4-aminoacetophenone, PABA, 3,4-DCA, the chloro-4-fluoroaniline of 3-or 5-amino-2-chlorobenzotrifluoride.
3. the synthetic method of according to claim 13,7-two aryl-1,5-dioxy-3,7-diazo-cyclooc-tanes, is characterized in that: described polar solvent is ethyl acetate.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3093631A (en) * | 1963-06-11 | Xnxch | ||
| CN1468245A (en) * | 2000-10-02 | 2004-01-14 | New process for the production of oxabispidines |
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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3093631A (en) * | 1963-06-11 | Xnxch | ||
| CN1468245A (en) * | 2000-10-02 | 2004-01-14 | New process for the production of oxabispidines |
Non-Patent Citations (3)
| Title |
|---|
| Eight-Membered Ring Heterocycles from Primary Amines, Hydrogen Sulfide and Formaldehyde;Nelson J.Leonard et al;《The Journal of Organic Chemistry》;19620630;第27卷;第2019-2021页 * |
| New Synthesis, X-ray Structural Determination, Conformational Analysis and Anomeric Effect Study of 3,7-Di(3-nitrophenyl)-1,5-Dioxa-3,7-Diazacyclooctane;A.Kakanejadifard et al;《J. Heterocyclic Chem.》;20061231;第43卷;第1695-1697页 * |
| 固体酸硅胶-磺酸在有机合成中的应用研究;俞建峰 等;《绍兴文理学院学报》;20101231;第30卷(第10期);第39-44页 * |
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