CN106117247B - A kind of preparation method of the cyclohexadione compounds of 2 methyl 1,2,3,9 tetrahydro benzo [b] pyrroles [1,4] thiazine 1,3 - Google Patents
A kind of preparation method of the cyclohexadione compounds of 2 methyl 1,2,3,9 tetrahydro benzo [b] pyrroles [1,4] thiazine 1,3 Download PDFInfo
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- CN106117247B CN106117247B CN201610494216.7A CN201610494216A CN106117247B CN 106117247 B CN106117247 B CN 106117247B CN 201610494216 A CN201610494216 A CN 201610494216A CN 106117247 B CN106117247 B CN 106117247B
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
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Abstract
The present invention relates to a kind of preparation method of the cyclohexadione compounds of 2 methyl 1,2,3,9 tetrahydro benzo [b] pyrroles [Isosorbide-5-Nitrae] thiazine 1,3, the structural formula of compound is：Prepare：Near amino thiophenols, N methylmaleimidos and catalyst are added in solvent, are passed through oxygen, 25 DEG C~160 DEG C is then heated to and reacts 4~24 hours, purification, produce.The diketone high income of 2 methyl 1,2,3,9 tetrahydro benzo [b] pyrroles [Isosorbide-5-Nitrae] thiazine 1,3 prepared by the present invention, operation is simple, and reaction scheme is short, oxidant green natural, and the generation three wastes are few, are easy to industrialized production.
Description
Technical field
The invention belongs to pharmaceutical intermediate and its preparation field, more particularly to a kind of 2- methyl isophthalic acids, 2,3,9- tetrahydro benzos
The preparation method of [b] pyrroles [1,4]-thiazine -1,3- cyclohexadione compounds.
Background technology
2- methyl isophthalic acids, 2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- diketone (I) and its derivative are important
Drug synthesis intermediate, while there is quite varied antibacterial activity, particularly there is certain suppression to Gram-negative bacteria
Make activity (Igarashi, Y.；Watanabe,S.Preparation of 1,4-benzothiazine-2,3-
dicarboximides via intramolecular cyclization of N-substituted 2-[(2-
acylaminophenyl)thio]maleimides and investigation of their antibacterial
activity.Nippon.Kagaku Kaishi.1992,11,1392-1396.)。
The synthetic method of document report 1,2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- cyclohexadione compounds
It is main to include three kinds：
Method one flows back in absolute ethyl alcohol using near amino thiophenols and N- phenyl -3,4- dichloros maleimides as raw material
2- phenyl -1,2,3,9- tetrahydro benzos [b] pyrroles's [Isosorbide-5-Nitrae]-thiazine -1,3- diketone, yield 77% is made in 15h.
(Katritzky,A.R.；Fan,W.Q.；Li,Q.L.；Bayyuk,S.Novel chromophoric heterocycles
based on maleimide and naphthoquinone.J.Heterocyclic.Chem.1989,26,885-892.)。
Using N- methyl -3- (2- acetylaminos thiophenyl), maleimide is raw material to method two, successively by molecule inner ring
Change the steps such as reaction, nucleophilic substitution reaction, elimination and hydrolysis, finally obtained 2- methyl isophthalic acids, 2,3,9- tetrahydro benzos [b] pyrrole
Cough up [1,4]-thiazine -1,3- diketone and carry out antibacterial activity research.(Igarashi,Y.；Watanabe,
S.Preparation of 1,4-benzothiazine-2,3-dicarbox-imides via intramolecular
cyclization of N-substituted 2-[(2-acylaminophenyl)thio]maleimides and
investigation of their antibacterial activity.Nippon.Kagaku Kaishi.1992,11,
1392-1396.)。
Method three is flowed back 1~2 hour in ethanol using near amino thiophenols and the bromo- N-phenylmaleimides of 3- as raw material
2- phenyl -1,2,3,9- tetrahydro benzos [b] pyrroles's [Isosorbide-5-Nitrae]-thiazine -1,3- diketone is made, yield is 50~55%.
(Zornikov,I.P.；Shikhaliev,Kh.S.；Kovygin,Yu.A.；Sabynin,A.L.；Zorina,A.V.Two
directions of reaction between aminothiophenol and 3-
bromoarylmaleimides.Russ.J.Org.Chem.2008,44(11),1736-1737.)；In above-mentioned three kinds of methods, side
The raw material of method one and method three is not easy to obtain, and is both needed to prepare by testing, the experimental procedure of method two is longer, low yield, and the three wastes
Problem is serious.
In summary, there is the shortcomings of reaction scheme is long, yield is low and raw material is not easy to obtain in the above method, give birth on a large scale
Cost is of a relatively high in production.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of 2- methyl isophthalic acids, 2,3,9- tetrahydro benzos [b] pyrroles [1,
4]-thiazine -1,3- cyclohexadione compounds and preparation method thereof, it is former as starting using near amino thiophenols and N- methylmaleimidos
Material, using DMF as solvent, using CuI as catalyst, heating response 12 hours under the conditions of 100~110 DEG C, then plus water stirs
10min, ethyl acetate extraction, decompression boil off solvent, 2- methyl isophthalic acids, 2,3,9- tetrahydro benzos [b] pyrrole are obtained with ethyl alcohol recrystallization
[Isosorbide-5-Nitrae]-thiazine -1,3- cyclohexadione compounds are coughed up, yield may be up to 80%.This method technique is simple, the reaction time is short, cost
Low, environment-friendly, purity and high income, it is adapted to industrialized production.
A kind of 2- methyl isophthalic acids of the present invention, 2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- diones chemical combination
Thing, the structural formula of the compound are：
A kind of 2- methyl isophthalic acids of the present invention, 2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- cyclohexadione compounds
Preparation method, including：Near amino thiophenols, N- methylmaleimidos and catalyst are added in solvent, are passed through oxygen work
For oxidant, it is then heated to 25 DEG C~160 DEG C and reacts 4~24 hours, purification, produce；Wherein near amino thiophenols, N- methyl
The mol ratio of maleimide and catalyst is 1.0:1.0~1:5:0.1~1.0.
The catalyst is the one or more in cuprous iodide, copper chloride, copper acetate.
The mol ratio of near amino thiophenols, N- methylmaleimidos and cuprous iodide is 1.0:1.0~1:5:0.1~
1.0。
The solvent is in N,N-dimethylformamide DMF, DMAC N,N' dimethyl acetamide DMA and dimethyl sulfoxide (DMSO) DMSO
It is one or more of.
The w/v of the near amino thiophenols and reaction dissolvent is 1 gram:1 milliliter~100 milliliters.
It is passed through the oxygen of an atmospheric pressure.
The purification is：Water is added to stir 3-5min, ethyl acetate extraction, organic phase is dry, decompression boils off solvent, carries out weight
Crystallization obtains.
N-phenylmaleimide is 1 gram with the w/v of water and ethyl acetate：4 milliliters~100 milliliters：4 milliliters
~100 milliliters.
Recrystallization solvent for use is 95% ethanol.
It is as follows specifically to prepare reaction equation：
The 2- methyl isophthalic acids of Scheme 1, the synthetic route of 2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- diketone
2- methyl isophthalic acids, the structural formula of 2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- diketone：
Fusing point：About 237~239 DEG C；
Character：Yellow solid；
2- methyl isophthalic acids, the nucleus magnetic hydrogen spectrum data of 2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- diketone are as follows：
1H NMR(400MHz,DMSO)δ:3.27 (s, 3H), 6.62 (s, 1H), 7.39 (t, J=7.3Hz, 1H), 7.49
(t, J=7.2Hz, 1H), 7.71-7.73 (m, 2H)
2- methyl isophthalic acids, the nuclear-magnetism carbon modal data of 2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- diketone are as follows：
13C NMR(101MHz,DMSO)δ:25.53,110.71,119.36,126.67,127.14,128.29,131.08,
132.40,138.15,148.75,168.77.
Beneficial effect
The present invention is preparing 2- methyl isophthalic acids, the process of 2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- diketone
In, with cuprous iodide, stannous chloride or cuprous bromide etc. for catalyst, the reaction time is shortened, reduces three wastes problem, and
Yield is higher.The preparation method initiation material is easy to get, and cost is low, and operation is simple, and reaction scheme is short, is easy to industrial metaplasia
Production.
Brief description of the drawings
Fig. 1 is compound 2- methyl isophthalic acids, and the nuclear-magnetism of 2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- diketone is total to
The hydrogen that shakes is composed；
Fig. 2 is compound 2- methyl isophthalic acids, and the nuclear-magnetism of 2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- diketone is total to
The carbon that shakes is composed.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
Take near amino thiophenols 1.3g (0.01mol), N- methylmaleimidos 1.1g (0.01mol), cuprous iodide
0.19g (0.001mol), add into 100mL round-bottomed flasks, be passed through oxygen, then add DMF (DMF)
10mL, 120 DEG C of reaction 8h of holding, reaction are finished, add water 30mL, stir 5 minutes, and ethyl acetate 50mL × 3 extract, organic relevant
Dry, 95% ethyl alcohol recrystallization obtains yellow solid 2- methyl isophthalic acids, 2,3,9- tetrahydro benzos [b] pyrroles's [Isosorbide-5-Nitrae]-thiazine -1,3- diketone
1.22g, yield 52.6%, mp:236~238 DEG C.
Embodiment 2
Take near amino thiophenols 5.0g (0.04mol), N- methylmaleimidos 8.9g (0.08mol), cuprous iodide
7.6g (0.04mol), add into 100mL round-bottomed flasks, be passed through oxygen, then add DMA (DMA)
60mL, 120 DEG C of reaction 12h of holding, reaction are finished, add water 100mL, stir 5 minutes, ethyl acetate 100mL × 3 extract, organic phase
Dry, 95% ethyl alcohol recrystallization obtains yellow solid 2- methyl isophthalic acids, 2,3,9- tetrahydro benzos [b] pyrroles's [Isosorbide-5-Nitrae]-thiazine -1,3- bis-
Ketone 7.8g, yield 85.3%, mp:237~240 DEG C.
Embodiment 3
Take near amino thiophenols 5.0g (0.04mol), N- methylmaleimidos 4.4g (0.04mol), cuprous iodide
3.8g (0.02mol), add into 100mL round-bottomed flasks, be passed through oxygen, then add DMF (DMF)
50mL, 120 DEG C of reaction 10h of holding, reaction are finished, add water 50mL, stir 5 minutes, and ethyl acetate 100mL × 3 extract, organic relevant
Dry, 95% ethyl alcohol recrystallization obtains yellow solid 2- methyl isophthalic acids, 2,3,9- tetrahydro benzos [b] pyrroles's [Isosorbide-5-Nitrae]-thiazine -1,3- diketone
7.4g, yield 80.5%, mp:237~239 DEG C.
Embodiment 4
Take near amino thiophenols 1.25g (0.01mol), N- methylmaleimidos 1.3g (0.012mol), cuprous iodide
0.38g (0.002mol), add into 100mL round-bottomed flasks, be passed through oxygen, then add dimethyl sulfoxide (DMSO) 20mL, protect
120 DEG C of reaction 12h are held, reaction is finished, and is added water 50mL, is stirred 5 minutes, and ethyl acetate 50mL × 3 are extracted, and organic phase is dried, and 95%
Ethyl alcohol recrystallization obtains yellow solid 2- methyl isophthalic acids, 2,3,9- tetrahydro benzos [b] pyrroles's [Isosorbide-5-Nitrae]-thiazine -1,3- diketone 1.7g, receives
Rate 73.5%, mp:235~237 DEG C.
Embodiment 5
Take near amino thiophenols 10.0g (0.08mol), N- methylmaleimidos 8.9g (0.08mol), stannous chloride
2.0g (0.02mol), add into 100mL round-bottomed flasks, be passed through oxygen, then add dimethyl sulfoxide (DMSO) 60mL, keep
120 DEG C of reaction 12h, reaction are finished, and are added water 50mL, are stirred 5 minutes, and ethyl acetate 100mL × 3 are extracted, and organic phase is dried, 95% second
Alcohol recrystallizes to obtain yellow solid 2- methyl isophthalic acids, 2,3,9- tetrahydro benzos [b] pyrroles's [Isosorbide-5-Nitrae]-thiazine -1,3- diketone 11.9g, yield
64.5%, mp:235~237 DEG C.
Embodiment 6
Take near amino thiophenols 5.0g (0.04mol), N- methylmaleimidos 5.0g (0.045mol), cuprous bromide
1.43g (0.01mol), add into 100mL round-bottomed flasks, be passed through oxygen, then add DMF (DMF)
50mL, 120 DEG C of reaction 10h of holding, reaction are finished, add water 50mL, stir 5 minutes, and ethyl acetate 80mL × 3 extract, organic relevant
Dry, 95% ethyl alcohol recrystallization obtains yellow solid 2- methyl isophthalic acids, 2,3,9- tetrahydro benzos [b] pyrroles's [Isosorbide-5-Nitrae]-thiazine -1,3- diketone
6.0g, yield 65.5%, mp:236~238 DEG C.
Embodiment 7
Take near amino thiophenols 10.0g (0.08mol), N- methylmaleimidos 8.9g (0.08mol), stannous chloride
2.0g (0.02mol), add into 100mL round-bottomed flasks, be passed through oxygen, then add DMF (DMF)
60mL, 100 DEG C of reaction 12h of holding, reaction are finished, add water 50mL, stir 5 minutes, and ethyl acetate 100mL × 3 extract, organic relevant
Dry, 95% ethyl alcohol recrystallization obtains yellow solid 2- methyl isophthalic acids, 2,3,9- tetrahydro benzos [b] pyrroles's [Isosorbide-5-Nitrae]-thiazine -1,3- diketone
10.3g, yield 56.1%, mp:235~237 DEG C.
Claims (7)
1. a kind of 2- methyl isophthalic acids, the preparation side of 2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- cyclohexadione compounds
Method, it is characterised in that：The structural formula of the compound is：
Preparation includes：By near amino thiophenols, N- methylmaleimidos and catalyst cuprous iodide, stannous chloride or protobromide
Copper is added in reaction dissolvent, is passed through oxygen, is then heated to 25 DEG C~160 DEG C and is reacted 4~24 hours, purification, produces；It is wherein adjacent
The mol ratio of aminothiophenol, N- methylmaleimidos and catalyst is 1.0:1.0~1.5:0.1~1.0.
2. a kind of 2- methyl isophthalic acids according to claim 1,2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- two
The preparation method of ketone compounds, it is characterised in that：The solvent is N,N-dimethylformamide DMF, N, N- dimethylacetamides
One or more in amine DMA and dimethyl sulfoxide (DMSO) DMSO.
3. a kind of 2- methyl isophthalic acids according to claim 1,2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- two
The preparation method of ketone compounds, it is characterised in that：The w/v of the near amino thiophenols and reaction dissolvent is 1 gram:1
Milliliter~100 milliliters.
4. a kind of 2- methyl isophthalic acids according to claim 1,2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- two
The preparation method of ketone compounds, it is characterised in that：It is passed through the oxygen of an atmospheric pressure.
5. a kind of 2- methyl isophthalic acids according to claim 1,2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- two
The preparation method of ketone compounds, it is characterised in that：The purification is：Water is added to stir 3-5min, ethyl acetate extraction, organic phase
Dry, boil off solvent, be recrystallized to give.
6. a kind of 2- methyl isophthalic acids according to claim 5,2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- two
The preparation method of ketone compounds, it is characterised in that：N-phenylmaleimide is 1 with the w/v of water and ethyl acetate
Gram：4 milliliters~100 milliliters：4 milliliters~100 milliliters.
7. a kind of 2- methyl isophthalic acids according to claim 5,2,3,9- tetrahydro benzos [b] pyrroles [1,4]-thiazine -1,3- two
The preparation method of ketone compounds, it is characterised in that：Recrystallization solvent for use is 95% ethanol.
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