CN106496146A - A kind of ionic liquid-catalyzed regulation and control synthetic method of the sulphonic acids of dihydroquinazoline ketone and Quinazol derivative - Google Patents

A kind of ionic liquid-catalyzed regulation and control synthetic method of the sulphonic acids of dihydroquinazoline ketone and Quinazol derivative Download PDF

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CN106496146A
CN106496146A CN201610907208.0A CN201610907208A CN106496146A CN 106496146 A CN106496146 A CN 106496146A CN 201610907208 A CN201610907208 A CN 201610907208A CN 106496146 A CN106496146 A CN 106496146A
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ionic liquid
sulphonic acids
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regulation
catalyzed
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宋智彬
陶端健
余治宇
陈美颖
何俊雄
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Jiangxi Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
    • C07D239/72—Quinazolines; Hydrogenated quinazolines
    • C07D239/86—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in position 4
    • C07D239/88—Oxygen atoms
    • C07D239/91—Oxygen atoms with aryl or aralkyl radicals attached in position 2 or 3
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a kind of ionic liquid-catalyzed regulation and control synthetic method of the sulphonic acids of dihydroquinazoline ketone and Quinazol derivative.The method produces dihydroquinazoline ketone and Quinazol derivative with aldehyde compound by cascade reaction controllable by anthranilamide or derivatives thereof with sulphonic acids ionic liquid as catalyst.Under the catalytic reaction condition for setting, up to 99%, the yield of dihydroquinazoline ketone and quinazolinone can reach 95% for the high conversion rate of raw material.Compared with prior art, the present invention is with " green solvent " ionic liquid as catalyst, without the need for excess oxygen agent and heavy metal catalyst, there are multiple advantages such as reaction condition is gentle, environmental friendliness, reaction selectivity height, product yield high, controllable synthesize, catalyst recovery is convenient, be a kind of eco-friendly new method for efficiently synthesizing.

Description

The sulphonic acids of a kind of dihydroquinazoline ketone and Quinazol derivative are ionic liquid-catalyzed Regulation and control synthetic method
Technical field
The present invention relates to method prepared by the selectivity of dihydroquinazoline ketone and Quinazol derivative, and in particular to a kind of The ionic liquid-catalyzed regulation and control synthetic method of the sulphonic acids of dihydroquinazoline ketone and Quinazol derivative.
Background technology
Dihydroquinazoline ketone and Quinazol derivative are important benzheterocycle Alkaloids, while being also important have The essential building blocks of machine intermediate and traditional Chinese medicine ingredients orixine, isofebrifugine, couroupitine A etc..Due to dihydroquinazoline ketone and quinoline Oxazoline ketone derivatives have good biologically active, not only have anticancer, antibacterial, the multiple pharmacological effect such as antiviral, can be with Use as herbicide etc., its purposes is quite varied.
According to raw materials used difference, quinazolinone synthetic method common at present mainly has：A. with ortho-aminobenzoic acid Or derivatives thereof be raw material；B. with anthranilo nitrile as raw material；C. with o-Halogen benzoic acids or derivatives thereof as raw material；D. with benzo Oxazinone is the methods such as raw material.In these methods, the aerobic condensation reaction using anthranilamide with aldehyde prepares quinoline azoles The pro-gaze of the strategy of quinoline ketone is more exposed to synthetic work person.For reason is that aldehyde compound compares other raw materials current, have Huge number, be easy to get and the advantage such as with low cost.Other raw materials such as acyl chlorides are compared, aldehyde compound is in synthesis benzheterocycle Reaction condition needed for compound is also gentleer, green.But experience condensation, two steps of cyclization are not only needed in course of reaction, The dihydroquinazoline assimilation compound for ultimately producing also needs the process for experiencing oxidative dehydrogenation obtain quinazolinone.Also do not have so far A kind of method that regulation and control dihydroquinazoline ketone that can be under same catalyst action and Quinazol derivative are generated respectively.
Content of the invention
It is an object of the invention to provide the sulphonic acids ionic liquid of a kind of dihydroquinazoline ketone and Quinazol derivative Catalysis regulation and control synthetic method, the method green, regulation and control under the effect of sulphonic acids ionic-liquid catalyst optionally prepare dihydro Quinazolinone and Quinazol derivative.
The present invention is achieved in that a kind of dihydroquinazoline ketone and the sulphonic acids ionic liquid of Quinazol derivative are urged Change regulation and control synthetic method, comprise the following steps：
It is former that step 1. is separately added into a certain amount of anthranilamide or derivatives thereof, aldehyde compound in reactor Material and sulphonic acids ionic-liquid catalyst, after adding solvent, are uniformly mixed；
Reactor is warming up to goal response temperature and starts to react by step 2., after reaction certain time, by thing in reactor Material is poured into water, static split-phase, suction filtration, and mixed solvent of the solid phase for obtaining further with ethanol with water is recrystallized, as Target product.Water is mutually mainly sulphonic acids ionic liquid, is ionic-liquid catalyst through the remaining thick liquid of vacuum distillation, Can be recycled after recovery.
Described goal response temperature is adjusted as needed, when needing to generate product dihydroquinazoline ketone, goal response Temperature is 20～60 DEG C；When needing to generate product Quinazol derivative, goal response temperature is 60～120 DEG C.
Described aldehyde compound include benzaldehyde, p-tolyl aldehyde, to cyanobenzaldehyde, o fluorobenzaldehyde, thiophene- 2- formaldehyde, pyrrole-2-aldehyde, hutanal, salicylide etc..
Preferably, the formula of described anthranilamide is：
Described raw material aldehyde compound is 1 with the mol ratio of anthranilamide or derivatives thereof:1～2, sulphonic acids The consumption of ionic liquid for raw material gross mass 1%～20%
Solvent in above-mentioned steps 1 is ethanol, butanol or polyethylene glycol.
The described reaction time is 2～48h.
Described sulphonic acids ionic liquid can be N- alkyl-N '-alkyl sulfonic acid imidazole salts, N, N, N- alkyl-N- alkyl Sulfonic acid quaternary ammonium salt, N, N, N ', N '-tetraalkyl-N, the ionic liquid of any one in N '-alkyl sulfonic acid quaternary ammonium salt, their knot Structure formula is：
N- alkyl-N '-alkyl sulfonic acid imidazole salts
N, N, N- alkyl-N- alkyl sulfonic acid quaternary ammonium salts
N, N, N ', N '-tetraalkyl-N, N '-alkyl sulfonic acid quaternary ammonium salt
R in above-mentioned formula1, R2, R3Methyl, ethyl, n-propyl, isopropyl, normal-butyl or branched butyl group is selected from, in above-mentioned formula Anion [X-] it is selected from acetate, trifluoroacetic acid root, tetrafluoroborate, bisulfate ion or nitrate anion.
N- alkyl-N '-alkyl sulfonic acid imidazole salts, N, N, N- alkyl-N- alkyl sulfonic acids quaternary ammonium salt or N, N, N ' ,-four alkane of N ' The synthetic method of base-N, N '-alkyl sulfonic acid quaternary ammonium salt is：
, by N- alkyl imidazoles, N, N, N, under-trialkylamine or tetramethylethylenediamine and alkyl sultone room temperature for step 1. Reaction 24～48 hours, the precipitation of appearance through suction filtration, then rinse repeatedly crude product using organic solvent and obtain acid inner salt.
Step 2. measure by mol ratio, by above-mentioned through acid inner salt respectively with acetic acid, trifluoroacetic acid, tetrafluoro boric acid, sulphur Acid or nitric acid carry out acid-base neutralization reaction, and course of reaction is separated after terminating and sloughs water, obtains final product N- alkyl-N '-alkane after vacuum drying Base sulfonic acid quaternary ammonium salt, N, N, N- alkyl-N- alkyl sulfonic acids quaternary ammonium salt or N, N, N ', N '-tetraalkyl-N, N '-alkyl sulfonic acid quaternary ammonium Ionic liquid.
According to obtained in said method, quinazolinone or dihydroquinazoline ketone compounds have following structure：
In above-mentioned formula, Y is selected from H, methyl, ethyl；R’1It is selected from methyl, ethyl, propyl group, pyridine radicals, thienyl, pyrrole radicals； R’2It is selected from H, methyl, halogenic substituent, alkoxyl, hydroxyl；R’3It is selected from H, methyl, halogenic substituent, alkoxyl, hydroxyl, ammonia Base；R’4It is selected from H, methyl, halogenic substituent, alkoxyl, hydroxyl, nitro, cyano group, trifluoromethyl；R’5It is selected from H, methyl, halogen Substituent, alkoxyl, hydroxyl, nitro, cyano group, trifluoromethyl, N, N '-dialkyl amino.
The beneficial effect of the invention is：Using " green solvent " ionic liquid as catalyst, from different temperatures and solvent, The purpose of regulation and control synthesizing dihydro quinazolinone and Quinazol derivative is reached, the efficiency of reaction has greatly improved, effectively Reduce the energy consumption of process, the conversion ratio of aldehyde reaches as high as 99%, the most high yield of dihydroquinazoline ketone and Quinazol derivative Rate is all up 95%.The inventive method has that reaction condition is gentle, operating procedure is simple, reaction selectivity is high, regulation and control product is received The high multiple advantages of rate, and without spent acid discharge of wastewater, green degree is high；Secondly, the sulphonic acids needed for the inventive method Ionic-liquid catalyst synthetic method more simple, high activity, can multiple recovery, thus the inventive method is a kind of efficient Environmental protection regulation and control synthesizing dihydro quinazolinone and the new method of Quinazol derivative.
Specific embodiment
Further illustrate the present invention by the following examples, but patent right is not limited to these embodiments.
Embodiment 1：
In 100mL reactors, benzaldehyde 5.3g (50mmol), anthranilamide 8g (60mmol) and sulfonic acid is added Class ionic-liquid catalyst 0.13g (1wt% of raw material gross mass), adds 50ml solvents, after being uniformly mixed, heat temperature raising To 60 DEG C of reaction 2h, reaction feed liquid is poured into water after terminating by reaction, standing, suction filtration separation product and ionic-liquid catalyst, Used ionic liquid can continue to serve as lower secondary response, the yield of 2- phenyl -3H- quinazoline-4-ones after vacuum distillation For 95%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR(400MHz,CDCl3) δ=11.58 (br s, 1H), 8.35-8.33 (d, J=8.0Hz, 1H), 8.08- 8.06 (m, 1H), 7.88-7.80 (m, 2H), 7.60-7.58 (m, 2H), 7.52 (t, J=8.0Hz, 1H) ppm.
13C NMR (100MHz, CDCl3) δ=163.83,149.47,134.92,132.79,131.67,129.06, 128.00,127.42,126.81,126.38,121.87ppm.
MS m/z[M+H]+calcd:222.0；found:222.1.mp:236-238℃,(lit.235-236℃)
Embodiment 2：
In 100mL reactors, in oxygen or air ambient, p-tolyl aldehyde 6g (50mmol), adjacent amino is added Benzamide 8g (60mmol) and sulphonic acids ionic-liquid catalyst 1.3g (10wt% of raw material gross mass), adds 50ml molten Agent, after being uniformly mixed, is heated to 70 DEG C of reaction 2h, and reaction feed liquid is poured into water after terminating by reaction, standing, suction filtration Separation product and ionic-liquid catalyst, used ionic liquid can continue to serve as lower secondary response, 2- after vacuum distillation The yield of p-methylphenyl -3H- quinazoline-4-ones is 90%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR(400MHz,CDCl3) δ=12.45 (br s, 1H), 8.14 (d, J=8.0Hz, 1H), 8.09 (d, J= 8.0Hz, 2H), 7.86-7.83 (m, 1H), 7.71 (d, J=8.0Hz, 1H), 7.52-7.46 (m, 1H), 7.34 (d, J= 8.0Hz,2H),2.38(s,3H)ppm.
MS m/z[M+H]+calcd:236.0；found:236.3.mp:256-257℃,(lit.254-256℃)
Embodiment 3：
In 100mL reactors, in oxygen or air ambient, add to cyanobenzaldehyde 6.5g (50mmol), adjacent ammonia Yl-benzamide 8g (60mmol) and sulphonic acids ionic-liquid catalyst 2.6g (20wt% of raw material gross mass), adds 50ml Solvent, after being uniformly mixed, is heated to 80 DEG C of reaction 2h, and reaction feed liquid is poured into water after terminating, stands, takes out by reaction Filter separation product and ionic-liquid catalyst, used ionic liquid can continue to serve as lower secondary response after vacuum distillation, 2- is 84% to the yield of cyano-phenyl -3H- quinazoline-4-ones.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR (400MHz, DMSO-d6) δ=12.75 (br s, 1H), 8.42-8.36 (m, 2H) 8.25-8.21 (m, 1H),8.12-8.08(m,1H),7.93-7.89(m,1H),7.83-7.81(m,1H),7.64-7.60(m,1H)ppm.
13C NMR (100MHz, DMSO-d6) δ=162.64,151.95,148.85,137.46,135.77,134.76, 132.98,129.30,128.13,127.66,127.78,126.35,121.71,118.80,114.06ppm.
MS m/z[M+H]+calcd:247.2；found:247.4.mp:exceed 300℃,(lit.291-293℃)
Embodiment 4：
In 100mL reactors, in oxygen or air ambient, o fluorobenzaldehyde 6.2g (50mmol), adjacent amino is added Benzamide 8g (60mmol) and sulphonic acids ionic-liquid catalyst 1.3g (10wt% of raw material gross mass), adds 50ml molten Agent, after being uniformly mixed, is heated to 80 DEG C of reaction 2h, and reaction feed liquid is poured into water after terminating by reaction, standing, suction filtration Separation product and ionic-liquid catalyst, used ionic liquid can continue to serve as lower secondary response, 2- after vacuum distillation The yield of o-fluorophenyl -3H- quinazoline-4-ones is 88%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR (400MHz, CDCl3) δ=8.45-8.41 (m, 1H), 8.36-8.32 (m, 1H), 7.87-7.82 (m, 1H),7.53-7.49(m,3H),7.41-7.37(m,2H)ppm.
MS m/z[M+H]+calcd:240.0；found:249.3.mp:234-236℃,(lit.231-233℃)
Embodiment 5：
In 100mL reactors, in oxygen or air ambient, thiophene -2-formaldehyde 5.6g (50mmol), adjacent amino is added Benzamide 8g (60mmol) and sulphonic acids ionic-liquid catalyst 0.6g (5wt% of raw material gross mass), adds 50ml solvents, After being uniformly mixed, 80 DEG C of reaction 2h are heated to, reaction feed liquid is poured into water after terminating by reaction, standing, suction filtration point From product and ionic-liquid catalyst, used ionic liquid can continue to serve as lower secondary response, 2- thiophenes after vacuum distillation The yield of fen base -3H- quinazoline-4-ones is 93%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR (400MHz, CDCl3) δ=12.65 (br s, 1H), 8.22 (d, J=3.0Hz, 1H), 8.12 (d, J= 8.0Hz, 1H), 7.86 (d, J=5.0Hz, 1H), 7.84-7.81 (m, 1H), 7.64 (d, J=8.0Hz, 1H), 7.48 (t, J= 8.0Hz,1H),7.26-7.22(m,1H)ppm.
MS m/z[M+H]+calcd:228.0；found:228.4.mp:277-278℃,(lit.275-276℃)
Embodiment 6：
In 100mL reactors, in oxygen or air ambient, pyrrole-2-aldehyde 4.7g (50mmol), adjacent amino is added Benzamide 8g (60mmol) and sulphonic acids ionic-liquid catalyst 1.2g (10wt% of raw material gross mass), adds 50ml molten Agent, after being uniformly mixed, is heated to 90 DEG C of reaction 2h, and reaction feed liquid is poured into water after terminating by reaction, standing, suction filtration Separation product and ionic-liquid catalyst, used ionic liquid can continue to serve as lower secondary response after vacuum distillation, obtain To mixed solvent of the solid phase further with ethanol with water recrystallized, obtain sterling 2- pyrrole radicals -3H- quinazoline-4-ones Yield be 84%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR (400MHz, DMSO-d6) δ=12.24 (br s, 1H), 11.77 (br s, 1H), 8.09 (d, J=4Hz, 1H), 7.77 (t, J=8.0Hz, 1H), 7.62 (d, J=4.0Hz, 1H), 7.41 (t, J=8.0Hz, 1H), 7.35-7.31 (m, 1H),7.06-7.02(m,1H),6.22-6.20(m,1H)ppm.
13C NMR (100MHz, DMSO-d6) δ=162.41,119.69,116.92,134.93,126.85,125.67, 124.73,124.33,120.92,112.97,110.21ppm.
MS m/z[M+H]+calcd:211.0；found:211.2.mp:271-272℃,(lit.274-274℃)
Embodiment 7：
In 100mL reactors, in oxygen or air ambient, hutanal 3.6g (50mmol), o-amino benzoyl is added Acid amides 8g (60mmol) and sulphonic acids ionic-liquid catalyst 1.1g (10wt% of raw material gross mass), adds 50ml solvents, stirs Mix after being well mixed, be heated to 100 DEG C of reaction 2h, reaction feed liquid is poured into water after terminating by reaction, and ethyl acetate is extracted, Organic phase concentration, column chromatography for separation obtain sterling, and water mutually can be continued to serve as down after vacuum distillation for used ionic liquid Secondary response, the yield of 2- n-propyl -3H- quinazoline-4-ones is 76%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR (400MHz, CDCl3) δ=12.01 (br s, 1H), 8.31 (d, J=8.0Hz, 1H), 7.75-7.71 (m, 2H), 7.49 (t, J=7.5Hz, 1H), 2.81 (t, J=7.5Hz, 2H), 1.95 (d, J=7.5Hz, 2H), 1.10 (t, J= 7.5Hz,3H)ppm.
13C NMR (100MHz, DMSO-d6) δ=162.36,157.74,149.40,135.67,127.25,126.31, 126.20,121.25,36.80,20.68,13.91ppm.
MS(ESI):m/z[M+H]+calcd:188.0；found:188.1.mp:190℃,(lit.190-192℃)
Embodiment 8：
In 100mL reactors, in oxygen or air ambient, m-methoxybenzaldehyde 6.8g (50mmol) is added, adjacent Aminobenzamide 15g (100mmol) and sulphonic acids ionic-liquid catalyst 1.3g (10wt% of raw material gross mass), adds 50ml solvents, after being uniformly mixed, are heated to 80 DEG C of reaction 2h, and reaction feed liquid is poured into water after terminating by reaction, quiet Put, suction filtration separation product and ionic-liquid catalyst, used ionic liquid can continue to serve as next time after vacuum distillation Reaction, the yield of 2- m-methoxyphenyl -3H- quinazoline-4-ones is 89%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments Data：
1H NMR(400MHz,CDCl3) δ=7.92-7.96 (m, 1H), 7.50-7.53 (m, 2H), 7.36-7.32 (m, 1H),6.99-6.95(m,3H),6.65(s,1H),3.85(s,3H)ppm.
13C NMR(100MHz,CDCl3) δ=164.89,160.96,147.37,134.02,130.60,128.78, 128.75,119.65,117.81,114.56,114.32,55.43ppm.
MS(ESI):m/z[M+H]+calcd:252.1；found:252.4.
Embodiment 9：
In 100mL reactors, in oxygen or air ambient, salicylide 6.1g (50mmol), o-amino benzoyl is added Acid amides 8g (60mmol) and sulphonic acids ionic-liquid catalyst 1.2g (10wt% of raw material gross mass), adds 50ml solvents, stirs Mix after being well mixed, be heated to 80 DEG C of reaction 2h, reaction feed liquid is poured into water after terminating by reaction, and standing, suction filtration are separated Product and ionic-liquid catalyst, used ionic liquid can continue to serve as lower secondary response, 2- neighbour's hydroxyls after vacuum distillation The yield of base phenyl -3H- quinazoline-4-ones is 96%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR (400MHz, DMSO-d6) δ=8.22-8.25 (m, 1H), 8.15-8.18 (m, 1H), 7.85-7.89 (m, 1H),7.76-7.78(m,1H),7.54-7.58(m,1H),7.44-7.48(m,1H),6.95-7.03(m,2H)ppm.
MS(ESI):m/z[M+H]+calcd:239.2；found:239.1
Embodiment 10：
In 100mL reactors, in oxygen or air ambient, 4- (N, N- diethyl amido) salicylide 10g is added (50mmol), anthranilamide 8g (60mmol) and sulphonic acids ionic-liquid catalyst 1.8g (raw material gross mass 10wt%), 50ml solvents are added, after being uniformly mixed, is heated to 80 DEG C of reaction 2h, reaction will react feed liquid after terminating It is poured into water, stands, suction filtration separation product and ionic-liquid catalyst, used ionic liquid can be after after vacuum distillation Continue and be used as lower secondary response, the yield of 2- (4 '-N, N- diethyl -2 '-hydroxy phenyl of amido) -3H- quinazoline-4-ones is 75%. It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR (400MHz, DMSO-d6) δ=8.00-8.09 (m, 2H), 7.76-7.80 (m, 1H), 7.59-7.61 (m, 1H), 7.40-7.44 (m, 1H), 6.29-6.31 (m, 1H), 6.11 (s, 1H), 3.40 (q, J=8Hz, 4H), 1.13 (t, J= 8Hz,6H)ppm.
MS(ESI):m/z[M+H]+calcd:310.3；found:310.5
Embodiment 11：
In 100mL reactors, in oxygen or air ambient, addition o-tolualdehyde 6g (50mmol), 2- amino- N-methyl-benzamide 9g (60mmol) and sulphonic acids ionic-liquid catalyst 1.5g (10wt% of raw material gross mass), adds 50ml solvents, after being uniformly mixed, are heated to 120 DEG C of reaction 6h, and reaction feed liquid is poured into water after terminating by reaction, quiet Put, suction filtration separation product and ionic-liquid catalyst, used ionic liquid can continue to serve as next time after vacuum distillation Reaction, the yield of 2- o-methyl-phenyl -3- methylquinazolin -4- ketone is 80%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments Data：
1H NMR(400MHz,CDCl3) δ=8.27-8.30 (m, 1H), 7.70-7.71 (m, 2H), 7.45-7.48 (m, 1H),7.33-7.35(m,1H),7.26-7.28(m,3H),3.28(s,3H),2.18(m,3H)ppm.
MS(ESI):m/z[M+H]+calcd:251.3；found:251.5.
Embodiment 12：
In 100mL reactors, in nitrogen or air ambient, benzaldehyde 5.3g (50mmol), o-amino benzoyl is added Acid amides 8g (60mmol) and sulphonic acids ionic-liquid catalyst 0.13g (1wt% of raw material gross mass), adds 50ml solvents, stirs Mix after being well mixed, reaction feed liquid is poured into water after terminating by 20 DEG C of reaction 24h, reaction, standing, suction filtration separation product and ion Liquid catalyst, used ionic liquid can continue to serve as lower secondary response, 2- phenyl -2,3- dihydro quinolines after vacuum distillation The yield of oxazoline -4- ketone is 95%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR(400MHz,CDCl3) δ=7.95 (d, J=8.0Hz, 1H), 7.63-7.59 (m, 2H), 7.48-7.45 (m, 3H), 7.34 (t, J=4.0Hz, 1H), 6.91 (t, J=8.0Hz, 1H), 6.68 (d, J=4.0Hz, 1H), 5.91 (s, 1H),5.81(br s,1H)ppm.
13C NMR (100MHz, DMSO-d6) δ=163.98,147.68,146.92,133.85,127.78,126.93, 117.98,115.58,115.17,63.02ppm.
MS(ESI):m/z[M+H]+calcd:224.0；found:224.2.mp:223-225℃,(lit.220-222℃)
Embodiment 13：
In 100mL reactors, in oxygen or air ambient, add to cyanobenzaldehyde 6.5g (50mmol), adjacent ammonia Yl-benzamide 8g (60mmol) and sulphonic acids ionic-liquid catalyst 2.6g (20wt% of raw material gross mass), adds 50ml molten Agent, after being uniformly mixed, reaction feed liquid is poured into water after terminating by 30 DEG C of reaction 24h, reaction, standing, suction filtration separation product With ionic-liquid catalyst, used ionic liquid can continue to serve as lower secondary response after vacuum distillation, and 2- is to cyano group benzene The yield of base -2,3- dihydroquinazoline -4- ketone is 86%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR (400MHz, DMSO-d6) δ=8.42 (s, 1H), 7.85 (d, J=4.0Hz, 2H), 7.66 (d, J= 4.0Hz, 2H), 7.62-7.58 (d, J=8.0Hz, 1H), 7.26-7.23 (m, 1H), 6.76 (d, J=4.0Hz, 1H), 6.68 (t, J=8.0Hz, 1H), 5.86-5.82 (m, 1H) ppm.
13C NMR (100MHz, DMSO-d6) δ=163.75,150.03,147.79,133.95,132.83,128.23, 127.81,119.06,117.06,115.79,114.97,111.95,66.04ppm.
MS(ESI):m/z[M+H]+calcd:249.0；found:249.1.mp 277-278℃
Embodiment 14：
In 100mL reactors, in oxygen or air ambient, o fluorobenzaldehyde 6.2g (50mmol), adjacent amino is added Benzamide 8g (60mmol) and sulphonic acids ionic-liquid catalyst 1.3g (10wt% of raw material gross mass), adds 50ml molten Agent, after being uniformly mixed, reaction feed liquid is poured into water after terminating by 40 DEG C of reaction 24h, reaction, standing, suction filtration separation product With ionic-liquid catalyst, used ionic liquid can continue to serve as lower secondary response after vacuum distillation, and 2- o-fluorophenyls- The yield of 2,3 dihydroquinazoline -4- ketone is 83%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR (400MHz, CDCl3) δ=7.96-7.91 (m, 1H), 7.68 (t, J=8.0Hz, 1H), 7.39-7.35 (m, 2H), 7.21 (t, J=8.0Hz, 1H), 7.11 (t, J=8.0Hz, 1H), 6.89 (t, J=8.0Hz, 1H), 6.68 (d, J= 4.0Hz,1H),6.31-6.29(m,1H),5.97(br s,1H)ppm.
13C NMR (100MHz, CDCl3) δ=161.42,116.70,134.70,131.17,128.68,126.59, 131.21,128.68,126.9,124.87,119.74,115.77,114.73,61.90ppm.
MS(ESI):m/z[M+H]+calcd:242.2；found:242.3.mp 223-224℃
Embodiment 15：
In 100mL reactors, in oxygen or air ambient, add positive propionic aldehyde 2.9g (50mmol), o-amino benzoyl Acid amides 8g (60mmol) and sulphonic acids ionic-liquid catalyst 1.0g (10wt% of raw material gross mass), adds 50ml solvents, stirs Mix after being well mixed, reaction feed liquid is poured into water after terminating by 50 DEG C of reaction 24h, reaction, and ethyl acetate is extracted, and organic phase is dense Contracting, column chromatography for separation obtain sterling, and water mutually can continue to serve as lower secondary response, 2- for used ionic liquid after vacuum distillation The yield of -2,3 dihydroquinazoline -4- ketone of ethyl is 75%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR(400MHz,CDCl3) δ=7.89 (d, J=4.0Hz, 1H), 7.31 (t, J=8.0Hz, 1H), 6.86 (t, J=8.0Hz, 1H), 6.67 (d, J=4.0Hz, 1H), 6.05 (br s, 1H), 4.88-4.82 (m, 1H), 1.84-1.80 (m, 2H), 1.06 (t, J=8.0Hz, 3H) ppm.
13C NMR(100MHz,CDCl3) δ=165.42,117.44,133.81,128.60,119.35,116.97, 114.70,66.44,28.61,8.29ppm.
MS(ESI):m/z[M+H]+calcd:176.1；found:176.1.mp:201-202℃
Embodiment 16：
In 100mL reactors, in oxygen or air ambient, m-methoxybenzaldehyde 6.8g (50mmol) is added, adjacent Aminobenzamide 8g (60mmol) and sulphonic acids ionic-liquid catalyst 1.3g (10wt% of raw material gross mass), adds 50ml Solvent, after being uniformly mixed, reaction feed liquid is poured into water after terminating by 60 DEG C of reaction 2h, reaction, standing, suction filtration separation product With ionic-liquid catalyst, used ionic liquid can continue to serve as lower secondary response, 2- meta-methoxies after vacuum distillation The yield of phenyl-dihydroquinazoline -4- ketone is 87%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR (400MHz, CDCl3) δ=7.95 (d, J=4.0Hz, 1H), 7.52 (d, J=4.0Hz, 2H), 7.36- 7.32 (m, 1H), 6.99-6.95 (m, 3H), 6.67 (d, J=4.0Hz, 1H), 3.85 (s, 3H) ppm.
13C NMR (100MHz, CDCl3) δ=164.89,160.96,147.37,134.02,130.60,128.78, 128.75,119.65,114.56,114.32,68.69,55.43ppm.
MS(ESI):m/z[M+H]+calcd:254.1；found:254.4.mp:232-233℃
Embodiment 17：
In 100mL reactors, in oxygen or air ambient, o-tolualdehyde 6g (50mmol), adjacent amino is added Benzamide 8g (60mmol) and sulphonic acids ionic-liquid catalyst 1.2g (10wt% of raw material gross mass), adds 50ml molten Agent, after being uniformly mixed, 20 DEG C reaction 2h, reaction terminate after will reaction feed liquid be poured into water, stand, suction filtration separation product with Ionic-liquid catalyst, used ionic liquid can continue to serve as lower secondary response after vacuum distillation, and 2- o-methyl-phenyls- The yield of dihydroquinazoline -4- ketone is 82%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR(400MHz,CDCl3) δ=7.95 (d, J=4.0Hz, 1H), 7.72 (d, J=8.0Hz, 1H), 7.35- 7.31 (m, 2H), 7.26-7.22 (m, 1H), 6.91 (t, J=8.0Hz, 1H), 6.69 (d, J=4.0Hz, 1H), 6.17 (s, 1H),5.77(s,1H),2.47(s,3H)ppm.
13C NMR(100MHz,CDCl3) δ=165.76,147.67,136.36,135.86,133.99,131.33, 129.72,128.02,127.68,126.01,119.67,115.02,114.76,65.90,18.01ppm.
MS(ESI):m/z[M+H]+calcd:238.1；found:238.3.mp:211-213℃,(lit.210-222℃)
Embodiment 18：
In 100mL reactors, in oxygen or air ambient, thiophene -2-formaldehyde 5.6g (50mmol), adjacent amino is added Benzamide 8g (60mmol) and sulphonic acids ionic-liquid catalyst 1.1g (10wt% of raw material gross mass), adds 50ml molten Agent, after being uniformly mixed, reaction feed liquid is poured into water after terminating by 20 DEG C of reaction 24h, reaction, standing, suction filtration separation product With ionic-liquid catalyst, used ionic liquid can continue to serve as lower secondary response after vacuum distillation, 2- thienyl -2, The yield of 3- dihydroquinazoline -4- ketone is 85%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR(400MHz,CDCl3) δ=7.90-7.92 (m, 1H), 7.34-7.39 (m, 2H), 7.21-7.22 (m, 1H),7.01-7.03(m,1H),6.90-6.92(m,1H),6.69-6.71(m,1H),6.20(s,1H)ppm.
MS(ESI):m/z[M+H]+calcd:229.3；found:229.1.
Embodiment 19：
In 100mL reactors, in oxygen or air ambient, addition o-tolualdehyde 6g (50mmol), 2- amino- N-methyl-benzamide 9g (60mmol) and sulphonic acids ionic-liquid catalyst 1.5g (10wt% of raw material gross mass), adds 50ml solvents, after being uniformly mixed, are heated to 60 DEG C of reaction 6h, and reaction feed liquid is poured into water after terminating by reaction, quiet Put, suction filtration separation product and ionic-liquid catalyst, used ionic liquid can continue to serve as next time after vacuum distillation Reaction, the yield of 2- o-methyl-phenyl -2- hydrogen -3- methylquinazolin -4- ketone is 80%.It is below the nuclear magnetic resonance of product, matter Spectrum experimental data：
1H NMR(400MHz,CDCl3) δ=7.97-7.99 (m, 1H), 7.40-7.42 (m, 1H), 7.28-7.29 (m, 1H),7.22-7.24(m,2H),6.84-6.88(m,1H),6.53-6.55(m,1H),2.82(s,3H),2.49(m,3H)ppm.
MS(ESI):m/z[M+H]+calcd:253.3；found:253.5.
Embodiment 20：
In 100mL reactors, in oxygen or air ambient, o-chlorobenzaldehyde 7g (50mmol), adjacent aminobenzene is added Formamide 8g (60mmol) and sulphonic acids ionic-liquid catalyst 1.3g (10wt% of raw material gross mass), adds 50ml solvents, After being uniformly mixed, 20 DEG C reaction 48h, reaction terminate after will reaction feed liquid be poured into water, stand, suction filtration separation product with from Sub- liquid catalyst, used ionic liquid can continue to serve as lower secondary response after vacuum distillation, 2- Chloro-O-Phenyl -2, and 3 The yield of dihydroquinazoline -4- ketone is 86%.It is below the nuclear magnetic resonance of product, Mass spectrometry experiments data：
1H NMR (400MHz, DMSO-d6) δ=8.19 (s, 1H), 7.64-7.66 (m, 2H), 7.47-7.50 (m, 1H), 7.38-7.40(m,1H),7.23-7.27(m,1H),6.98-7.00(m,1H),6.69-6.77(m,2H),6.13(s,1H) ppm.
MS(ESI):m/z[M+H]+calcd:257.7；found:257.3. .

Claims (6)

1. the ionic liquid-catalyzed regulation and control synthetic method of the sulphonic acids of a kind of dihydroquinazoline ketone and Quinazol derivative, including with Lower step：
Step 1. be separately added in reactor a certain amount of anthranilamide or derivatives thereof, aldehyde compound raw material and Sulphonic acids ionic-liquid catalyst, after adding solvent, is uniformly mixed；
Reactor is warming up to goal response temperature and starts to react by step 2., after reaction certain time, material in reactor is fallen Enter in water, static split-phase, suction filtration, mixed solvent of the solid phase for obtaining further with ethanol with water is recrystallized, as target Product；
Wherein, described goal response temperature is adjusted as needed, when needing to generate product dihydroquinazoline ketone, goal response Temperature is 20～60 DEG C；When needing to generate product Quinazol derivative, goal response temperature is 60～120 DEG C.
2. the ionic liquid-catalyzed regulation and control of the sulphonic acids of dihydroquinazoline ketone according to claim 1 and Quinazol derivative Synthetic method, it is characterised in that：Raw material aldehyde compound is 1 with the mol ratio of anthranilamide or derivatives thereof:1～2.
3. the ionic liquid-catalyzed regulation and control of the sulphonic acids of dihydroquinazoline ketone according to claim 1 and Quinazol derivative Synthetic method, it is characterised in that：The consumption of sulphonic acids ionic liquid for raw material gross mass 1%～20%.
4. the ionic liquid-catalyzed regulation and control of the sulphonic acids of dihydroquinazoline ketone according to claim 1 and Quinazol derivative Synthetic method, it is characterised in that：Solvent selected from ethanol, butanol or polyethylene glycol described in step 1.
5. the ionic liquid-catalyzed regulation and control of the sulphonic acids of dihydroquinazoline ketone according to claim 1 and Quinazol derivative Synthetic method, it is characterised in that：The described reaction time is 2～48h.
6. the ionic liquid-catalyzed regulation and control of the sulphonic acids of dihydroquinazoline ketone according to claim 1 and Quinazol derivative Synthetic method, it is characterised in that：Described sulphonic acids ionic liquid can be N- alkyl-N '-alkyl sulfonic acid imidazole salts, N, N, N- Alkyl-N- alkyl sulfonic acid quaternary ammonium salts, N, N, N ', N '-tetraalkyl-N, the ionic liquid of any one in N '-alkyl sulfonic acid quaternary ammonium salt Body, their structural formula is：
N- alkyl-N '-alkyl sulfonic acid imidazole salts
N, N, N- alkyl-N- alkyl sulfonic acid quaternary ammonium salts
N, N, N ', N '-tetraalkyl-N, N '-alkyl sulfonic acid quaternary ammonium salt
R in above-mentioned formula1, R2, R3Be selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl or branched butyl group, in above-mentioned formula cloudy from Son [X-] it is selected from acetate, trifluoroacetic acid root, tetrafluoroborate, bisulfate ion or nitrate anion.
CN201610907208.0A 2016-10-18 2016-10-18 A kind of ionic liquid-catalyzed regulation and control synthetic method of the sulphonic acids of dihydroquinazoline ketone and Quinazol derivative Pending CN106496146A (en)

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CN110372611B (en) * 2019-07-24 2021-05-04 常熟理工学院 Method for selectively synthesizing polysubstituted dihydro quinazolinone or quinazolinone
CN115433134A (en) * 2022-09-16 2022-12-06 哈尔滨工业大学（深圳） Catalytic enantioselective synthesis method of dihydro quinazolinone

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