CN1626518A - Method for synthesizing ramification in benzamide class of pyridyl - Google Patents
Method for synthesizing ramification in benzamide class of pyridyl Download PDFInfo
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- CN1626518A CN1626518A CN 200310120428 CN200310120428A CN1626518A CN 1626518 A CN1626518 A CN 1626518A CN 200310120428 CN200310120428 CN 200310120428 CN 200310120428 A CN200310120428 A CN 200310120428A CN 1626518 A CN1626518 A CN 1626518A
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Abstract
A process for synthesizing N-pyridylbenzoylamine derivative features that the substituted benzoylamine derivativeand substituted nitropyridine compound as raw materials, Se as catalyst, and 1,8-diazabicycle [5,4,0]-+-carbon-7-ene as cocatalyst take part in reaction in organic solvent in high-pressure reactor under existance of Co.
Description
Technical field
The present invention relates to the synthetic of N-pyridyl benzamide derivatives, relate in particular to a kind of method of selenium catalyzed carbonylation, be used for synthetic N-pyridyl benzamide derivatives.
Technical background
(N-pyridyl benzamide derivatives CONH-) has certain bio-physiological activity to contain peptide bond.As N-benzoyl-N '-pyridyl carbamide derivative is class efficient pesticides [document: US4,405,552; EP8,880; DE3,126,263; US4,264,605; JP62,155,260; JP55,011,537; CA1,131,232 etc.]; N-phenyl-N '-pyridyl carbamide derivative is a class significant herbicide and plant-growth regulator [document: EP401,168; US438,054; The communication of plant physiology, 1989, (1), 17～19 etc.]; N-phenyl-N '-nitrogen pyridine oxide base carbamide derivative is class plant-growth regulator [document: US4,787,931 efficiently too; WO8,702,665; WO8,403,884 etc.].The method of conventional synthetic N-pyridyl benzamide derivatives mainly adopts the isocyanic ester method of phosgene or class phosgene at present, its weak point is that phosgene has severe toxicity, produce the big chloride by-product of macro-corrosion in the reaction process, not only the also easy contaminate environment of severe corrosion equipment.And the method for conventional synthetic N-pyridyl benzamide derivatives mainly adopts the method for three-step-march, the obvious complex operation of these class methods, and total recovery is also not too high.Document [Tetrahedron Lett, 1999,40 (26), 4845～4846; Chinese patent application number 01103688.5; Chinese patent application 01134394.X; Chinese patent application number 02109056.5] reported the preparation method of asymmetric replacement urea, but also be not used in preparation N-pyridyl benzamide derivatives.
Summary of the invention
The object of the present invention is to provide a kind of reaction conditions gentleness, the synthetic N-pyridyl benzamide derivatives of selenium catalysis simply and easily.
For achieving the above object, technical scheme of the present invention is as follows: in the presence of CO, with the benzamide derivatives of replacement and the nitropyridine compounds of replacement is raw material, with selenium is catalyzer, 1, and 8-diaza-bicyclo [5,4,0]-organic basess such as 11-carbon-7-alkene and triethylamine are promotor, react in the autoclave of sealing in organic solvent, replace one-step synthesis purpose product by the reduction of selenium catalyzed carbonylation; Reaction formula is as follows:
Wherein:
Substituent R on the nitropyridine
1Can be one or more inertia groups or be hydrogen atom; Nitro can be positioned at the position of substitution variant on the pyridyl; Substituent R on the benzamide derivatives
2Can be one or more gives electronics and/or electron-withdrawing group or is hydrogen atom; The mole dosage of catalyzer is 0.1～20% of a substrate; Organic bases can be triethylamine, 1,8-diaza-bicyclo [5,4,0]-11-carbon-7-alkene, 1,5-diaza-bicyclo [4,3,0]-5-nonene, 1,4-diaza-bicyclo [2,2,2] octane, N-crassitude or TERTIARY BUTYL AMINE etc., its mole dosage is 10～200% of a reaction substrate; The mol ratio of reaction substrate and solvent is 1: 1 to 1: 50; Reaction times is 2～20 hours; Temperature of reaction is 50～200 ℃; Reaction of carbon monoxide pressure is gauge pressure 1～10.0MPa.Substituent R on the wherein said reactant nitropyridine base
1Can be alkyl, alkoxyl group, alkylthio, dialkylamino etc.; R in the reactant organic amine
2For giving electron substituent group can be methyl, ethyl etc., and electron-withdrawing substituent can be trifluoromethyl, formyl radical, ethanoyl and halogen etc.; Wherein said CO also can be the industrial tail gas that contains CO; Organic solvent can be polarity or non-polar solvent, and polar solvent is toluene, tetrahydrofuran (THF), N, N '-dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) or chloroform etc., and non-polar solvent is normal hexane or benzene etc.
The present invention has following advantage:
1. cost is low.Catalyzer is inexpensive, and facility investment is few, easily operation.
2. reaction conditions gentleness.Do not use deleterious phosgene, the three wastes are few, production easy to clean.
3. catalyzer is recyclable uses again.
Specific implementation method
Below by embodiment in detail the present invention is described in detail; But the present invention is not limited to following embodiment.
Synthesizing of N-under the embodiment 1 selenium catalysis (6-methoxyl group-3-pyridyl) benzamide
In the stainless steel autoclave of 100ml, add 2-methoxyl group-5-nitropyridine (10mmol), selenium (0.5mmol), benzamide (10mmol), 1,8-diaza-bicyclo [5,4,0]-11-carbon-7-alkene (10mmol), triethylamine (20mmol) and toluene 10ml, with after the CO displacement three times CO pressure is risen to 3.0MPa, put it in 160 ℃ the oil bath pan stirring reaction 4 hours, be chilled to room temperature, reaction product is filtered, filter gained crystal purifying behind column chromatography, elutriant is a sherwood oil: ethyl acetate (10: 1), and concentrate eluant gets product, m.p.136-138 ℃, yield is 76%.
N-pyridyl benzamide derivatives is synthetic under the embodiment 2 selenium catalysis
Embodiment is summarized as follows with tabulated form: (its reaction conditions and step are with embodiment 1)
Table 1: the synthetic N-pyridyl benzamide derivatives of 2-methoxyl group-5-nitropyridine and benzamide derivatives reaction is synthetic under the selenium catalysis
Product is molten
Sequence number substrate product productive rate (%)
The point (℃)
1
136-138 76
2
119-120 80
3
102-103 81
4
168-169 84
5
134-136 87
6
112-114 49
7
196 68
8
174-176 42
N-pyridyl benzamide derivatives is synthetic under the embodiment 3 selenium catalysis differential responses conditions, with the example that synthesizes of N-(6-methoxyl group-3-pyridyl) benzamide, the result of implementation of (its reactions steps is with embodiment 1) is listed in table 2 under reaction conditionss such as different reaction ratios, reaction times, pressure, temperature.But the present invention is not limited to following embodiment.
Table 2: conditions such as the character of temperature of reaction, catalyst levels, alkali and consumption, CO pressure and reaction times are to the influence of reaction
Sequence number temperature catalysis metering alkali CO stress reaction time productive rate
(℃) (mmol) (mmol) (MPa) (h) (％)
9 110 0.5 TEA(20)+DBU(10) 3.0 4 69
11 160 0.01 TEA(20)+DBU(10) 3.0 4 66
12 160 1.0 TEA(20)+DBU(10) 3.0 4 78
13 160 0.5 TEA(/)+DBU(10) 3.0 4 62
15 160 0.5 TEA(20)+DABCO 3.0 4 71
(10)
17 160 0.5 TEA(20)+DBU(10) 1.0 4 57
18 160 0.5 TEA(20)+DBU(10) 5.0 4 75
19 160 0.5 TEA(20)+DBU(10) 3.0 1 72
20 160 0.5 TEA(20)+DBU(10) 3.0 10 75
Reaction conditions: 2-methoxyl group-5-nitropyridine, 10mmol; Benzamide, 10mmol; Organic bases, 0-20mmol; CO, 1.0-5.0MPa; Toluene, 10ml; Temperature, 110-160 ℃; Reaction times, 1.0-10.0h.
TEA: triethylamine (Triethylamine)
DABCO:1,4-diaza-bicyclo [2,2,2] octane (1,4-Diazabicyclo[2,2,2] octane)
DBU:1,8-diaza-bicyclo [5,4,0]-11 carbon-7-alkene (1,8-Diazabicyclo[5,4,0] undec-7-ene)
Claims (8)
1, a kind of method of synthetic N-pyridyl benzamide derivatives, the nitropyridine that replaces in the presence of CO and the benzamide derivatives of replacement are raw material, with selenium is catalyzer, and organic bases is a promotor, reacts in enclosed autoclave in organic solvent; Reaction formula is as follows:
Reaction product is filtered, and the gained crystal is with recrystallization or column chromatography purification;
Wherein:
Substituent R on the nitropyridine
1For one or more inertia groups or be hydrogen atom;
Nitro is positioned at the position of substitution variant on the pyridyl on the nitropyridine;
Substituent R on the benzamide derivatives that replaces
2For one or more are given electronics and/or electron-withdrawing group or are atom;
The mole dosage of catalyzer selenium is 0.1～20% of a substrate;
Its mole dosage of promotor is 10～200% of a reaction substrate, wherein 1, and the mol ratio of 8-diaza-bicyclo [5,4,0]-11-carbon-7-alkene and triethylamine is 1: 1 to 1: 5;
The mol ratio of reaction substrate and solvent is 1: 1 to 1: 50;
Reaction times is 2～20 hours;
Temperature of reaction is 50～200 ℃;
Reaction of carbon monoxide pressure is gauge pressure: 1～10.0Mpa.
2, by the described synthetic method of claim 1, it is characterized in that described substituent R
1Be alkyl, alkoxyl group, alkylthio or dialkylamino.
3, by the described synthetic method of claim 1, it is characterized in that described substituent R
2Be methyl, ethyl, trifluoromethyl, formyl radical, ethanoyl or halogen.
4, by the described synthetic method of claim 1, it is characterized in that, described carbon monoxide is the industrial carbon monoxide tail gas that contains air, nitrogen, carbonic acid gas and/or water vapor, and wherein the content sum of air, nitrogen, carbonic acid gas and/or water vapor is not more than 10% of cumulative volume.
5, by the synthetic method of the described N-pyridyl of claim 1 benzamide derivatives, it is characterized in that described organic solvent is toluene, tetrahydrofuran (THF), N, N '-dimethyl formamide, dimethyl sulfoxide (DMSO), chloroform, hexane or benzene.
6, by the described synthetic method of claim 1, it is characterized in that described promotor is a triethylamine, 1,8-diaza-bicyclo [5,4,0]-and 11-carbon-7-alkene, 1,5-diaza-bicyclo [4,3,0]-and 5-nonene, 1,4-diaza-bicyclo [2,2,2] octane, N-crassitude or TERTIARY BUTYL AMINE.
7, by the described synthetic method of claim 1, it is characterized in that, when described product is used recrystallization purifying, used solvent be the aqueous solution, dehydrated alcohol, trichloromethane of 60% dehydrated alcohol or/and N, dinethylformamide.
8, by the described synthetic method of claim 1, it is characterized in that, when described product uses column chromatography purifying, use unmodified packed column, be leacheate with sherwood oil and ethyl acetate or toluene and ethyl acetate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113264844A (en) * | 2021-06-01 | 2021-08-17 | 宿州学院 | Method for preparing aryl amide compound by catalyzing carbonylation of aryl tertiary amine through metal-free catalytic system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1294123A (en) * | 1999-10-20 | 2001-05-09 | 中国科学院大连化学物理研究所 | Catalytic synthesis process of asymmetric aryl substituted carbamide compounds |
| CN1156450C (en) * | 2001-02-09 | 2004-07-07 | 中国科学院大连化学物理研究所 | Process for preparing unsymmetric phenylpyridyl substances |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113264844A (en) * | 2021-06-01 | 2021-08-17 | 宿州学院 | Method for preparing aryl amide compound by catalyzing carbonylation of aryl tertiary amine through metal-free catalytic system |
| CN113264844B (en) * | 2021-06-01 | 2023-05-02 | 宿州学院 | Method for preparing aryl amide compound by catalyzing carbonylation of aryl tertiary amine without metal catalytic system |
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