CN108558625A - Boron trifluoride is catalyzed the synthetic method of benzophenone compound - Google Patents
Boron trifluoride is catalyzed the synthetic method of benzophenone compound Download PDFInfo
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- CN108558625A CN108558625A CN201810302005.8A CN201810302005A CN108558625A CN 108558625 A CN108558625 A CN 108558625A CN 201810302005 A CN201810302005 A CN 201810302005A CN 108558625 A CN108558625 A CN 108558625A
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- boron trifluoride
- benzophenone compound
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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Abstract
The present invention provides a kind of synthetic method of boron trifluoride catalysis benzophenone compound, specifically substituted benzoic acid, resorcinol derivatives and catalyst boron trifluoride ether are added in reaction vessel, gradually it is warming up to 95 120 DEG C, after reacting 10min 30min, it is dissolved with ethyl acetate, equivalent saturated sodium bicarbonate washs, benzophenone compound is obtained after dry, recrystallization, decoloration, technical solution using the present invention is easy to operate, using substituted benzoic acid and resorcinol derivatives as raw material one-step synthesis, production cost is reduced；Reaction condition is mild；By-product is water, environmentally friendly, and atom utilization is high；Post-reaction treatment is simple, and yield is up to 90% or more.
Description
Technical field
The present invention relates to the synthetic methods that boron trifluoride is catalyzed benzophenone compound.The present invention is to solve existing two
Benzophenone class compound synthesis method has that environmental pollution is big, of high cost low with yield.
Background technology
Benzophenone is the intermediate of ultra-violet absorber, organic pigment, medicine, fragrance, insecticide.Benzophenone first
Be ultraviolet absorber it is free radical (II) photoinitiator, is mainly used for free radical ultraviolet light solidification varnish system, such as UV coating, UV
Ink, UV adhesives etc., while uvioresistant ingredient is also can be used as in sun-proof serial cosmetics.Secondly in medical industry
For producing the drugs such as perhexiline, benzatropine hydrobromate, diphenhydramine hydrochloride.Benzophenone is also benzene second again
Alkene polymerization inhibitor and fragrance fixastive can assign breath of the essence with sweet tea, be used in a variety of perfume and fragrance for detergents, it is also possible to
In food flavors such as allotment almond, peach, cream, coconuts.
Benzophenone primary synthetic methods have following a few classes at present：Classical Friedel-Crafts reaction synthesis process, has
Following case.[J.Beger, et al.Synthese the von 4-Alkoxy-2- such as Beger
hydroxyphenylketoximen als Metallextraktions‐Reagenzien.Advanced Synthesis&
Catalysis,1992,334(3):269-277.] it reports and is urged with Lewis sour (such as aluminium chloride, zinc chloride or ferric trichloride)
Change chlorobenzoyl chloride and synthesize benzophenone with resorcinol, but synthetic yield is not high (80% or so), product colour is deeper, needs to take off
Color processing, it is maximum the disadvantage is that generation spent acid solid catalyst, hydrogen chloride gas and low-concentration hcl, bring all for three-protection design
It is mostly inconvenient.Sarvesh Kumar etc. [Sarvesh Kumar, et al.Arylalkyl Ketones, Benzophenones,
Desoxybenzoins and halcones Inhibit TNF-a Induced Expression of ICAM-1:
Structure-Activity Analysis.Arch. Pharm.Chem.Life Sci.2012,345,368-377.] report
With benzene and 2,4- dihydroxybenzoyl chlorine carries out Friedel-Crafts reactions and prepares benzophenone, but acyl chlorides cost is higher,
And by-product still has hydrogen chloride, does not solve the problems, such as fundamentally environmental-friendly.Using [Synthesis such as aluminium chloride
1991,4,322-324； Justus LiebigsAnnalen der Chemie 1913,398,137-196；
CN201010189053； CN200910063442；CN201310044918] benzotrichloride is catalyzed with resorcinol compared with low temperature
The lower reaction of degree, then UV-0 is obtained after hydrolyzing, the process costs are relatively low, high income, but coloured product is deeper, generate a large amount of exhaust gas
Environment is polluted with spent acid.Also there is document report using resorcinol and benzonitrile [Chemistry of Heterocyclic
Compounds 2015,50,1616-1623], benzoic acid derivative [Organic Preparations and Procedures
International 1992,24,687-690] or benzaldehyde [Zhang C.Y., et al. Hypervalent iodine
in synthesis 59:Application of polymeric diaryliodonium salts as aryl
Transfer reagents in SPOS.Synlett 2000,8,1175-1177.] it is the new side that raw material prepares benzophenone
Method, the intermolecular dehydrogenation that such method realizes different carbonyls and benzene by transition metal are coupled, and Atom economy is high,
It is the new approaches of organic synthesis field, but the catalyst for needing costliness, and complicated for operation more, the reaction time is long, and yield is medium,
Cost of material is higher.
Boron trifluoride ether is used as the catalysis of acetylation, alkylation, polymerization, dehydration and condensation reaction in organic synthesis
Agent.On this basis, it is the high-efficiency synthesis method of discussion benzophenone derivates, uses boron trifluoride ether for catalyst, with
Phase, which obtains, is concisely and efficiently synthetic method, reduces production cost and synthesis difficulty.
Invention content
The present invention is to solve existing synthesis benzophenone compound method there are environmental pollutions big, of high cost and yields
Low problem, and a kind of new process for catalytic synthesis provided.Realizing the technical solution of the object of the invention is：With substituted benzene
Formic acid and resorcinol derivatives are raw material, and Friedel-Crafts reaction systems occur under boron trifluoride ether existence condition
Standby benzophenone derivates.This method is synthesized with the solvent-free catalytic one-stage of boron trifluoride ether, reduces equipment cost；By-product
Environmentally friendly for water, atom utilization is high；Post-reaction treatment is simple, and yield is up to 90% or more；It reacts solvent-free, and urges
Agent can reduce cost with recovery, be suitble to industrialized production.
Specific implementation step is as follows：Substituted benzoic acid and resorcinol derivatives are added in boron trifluoride ether,
0.5h is reacted under 110 DEG C of temperature and stirring condition, solvent boron trifluoride ether is evaporated off, the sodium bicarbonate that residue is saturated is washed
Residual solvent is washed, is recrystallized with first alcohol and water, activated carbon decolorizing is to get target product.Wherein, the use of raw material and catalyst rubs
You are than being substituted benzoic acid：Resorcinol derivatives：Boron trifluoride ether=1:1:0.4.
The reaction formula that the present invention synthesizes benzophenone compound is as follows：
The present invention has the following advantages：
(1) easy to operate, using substituted benzoic acid and resorcinol derivatives as raw material one-step synthesis, reduces and be produced into
This.
(2) reaction condition is mild.
(3) by-product is water, environmentally friendly, and atom utilization is high.
(4) post-reaction treatment is simple, and yield is up to 90% or more.
(5) reaction is using catalyst as solvent, and catalyst can reduce cost with recovery, is suitble to industrialized production.
Description of the drawings
The hydrogen that Fig. 1 is compound 3a is composed.
The hydrogen that Fig. 2 is compound 3b is composed.
Specific implementation mode
Embodiment 1
Experimental section
Reagent and equipment
Benzoic acid, resorcinol, ethyl acetate, petroleum ether, boron trifluoride ether are analytical reagents.Laboratory apparatus packet
It includes X-4 numbers and shows micro melting point apparatus, SHB-IIIA multiplex vavuum pump of circulating water type, Bruker AV 400-MHz nuclear-magnetisms
Resonance spectrometer, 330 type infrared spectrometers of AVATAR, EYELA SB-1100 Rotary Evaporators etc..
Experimental procedure
By resorcinol, o-bromobenzoic acid and boron trifluoride ether are added in three mouthfuls of reaction bulbs of 1L, temperature reaction,
TLC contact plates monitor, and after complete reaction, steam solvent, are dissolved with a small amount of ethyl acetate, the bicarbonate being successively saturated with equivalent
The brine It of sodium, saturation separates organic layer, dry, steams ethyl acetate, obtains yellowish crude product.Pouring into proper amount of methanol
It is recrystallized in distilled water, obtains white solid.
Conditional filtering
The screening of 1 reaction condition of tablea
aReaction condition：O-bromobenzoic acid 1a (2mmol), resorcinol 2a (2mmol)bRecrystallize yield
It is found according to experiment, can be increased with the raising yield of temperature, but in view of industrial production safety, by temperature highest
110 degrees Celsius of positioning.But extend the reaction time to increase side reaction, influence yield.So selecting catalyst equivalent is 0.4
Times, reaction temperature is 110 DEG C, and time 25min is optimum reaction condition.
Embodiment 1：By o-bromobenzoic acid (122g, 1.0mol), resorcinol (110g, 1.0mol) and boron trifluoride second
Ether (56.8g, 0.4mol) is added in three mouthfuls of reaction bulbs of 1L, is gradually warming up to 110 DEG C, is reacted 0.5 hour, is steamed solvent,
It is dissolved with a small amount of ethyl acetate, the sodium bicarbonate being saturated with equivalent washs, and separates organic layer, dry, steams ethyl acetate, obtains yellow
Color crude product.It is recrystallized in pouring into proper amount of methanol and distilled water, with activated carbon decolorizing, obtains white solid 276.4g, yield
95%.Wherein catalyst boron trifluoride ether rate of recovery ＞ 60%, ethyl acetate rate of recovery ＞ 98%, first alcohol and water rate of recovery ＞
98%, product comprehensive yield ＞ 93%.
On this basis, the aryl such as o-iodobenzoic acid, acetylsalicylic acid, P-hydroxybenzoic acid, benzoic acid have been expanded respectively
Carboxylic acid, reacted under the catalysis of catalyst boron trifluoride ether with resorcinol or p-methyl phenol respectively (substituted benzoic acid,
Fortified phenol, boron trifluoride ether the ratio between the amount of substance be 1：1：0.4), operation is executed according to implementing 1, can be obtained in high yield
To target product.
2 reaction substrate of table is expanded
Structural characterization
Experiment reagent and instrument：Deuterochloroform, deuterated dimethyl sulfoxide (D-atom content 99.8%, TMS contents 0.03%V/
V, 10*0.5mL/ box, ARMAR companies of Switzerland)；Nuclear magnetic tube (2 ST500-8 of 5mm 100/pk, Norell companies of the U.S.).
Ultrashied 400MHz Plus Nuclear Magnetic Resonance (Bruker companies of Switzerland)
Test process：10mg target compounds accurately are weighed, it is sub- with 0.5mL deuterochloroforms or deuterated diformazan in nuclear magnetic tube
Sulfone dissolves, its chemical constitution is tested by Nuclear Magnetic Resonance.
3a：Fusing point：143.6 DEG C, white solid, Rf=0.5 (petroleum ether:Ethyl acetate=3:1)
1H NMR(400MHz,Chloroform-d)δ12.36(s,1H),7.65-7.60(m,2H), 7.99-7.63(m,
2H), 7.41-7.25 (m, 3H), 6.44 (s, 1H), 6.30 (d, J=8.2Hz, 1H)
13C NMR(101MHz,Chloroform-d)δ200.35,166.03,163.11,138.04,136.16,
131.58,128.80,128.33,113.35,107.76,103.61.
3b：Fusing point：148.9 DEG C, yellowish white powder, Rf=0.5 (petroleum ether:Ethyl acetate=3:1)
1H NMR(400MHz,Chloroform-d)δ12.36(s,1H),8.07-7.90(m,2H),7.47-7.06(m,
4H), 6.45 (d, J=2.3Hz, 1H), 6.30 (dd, J=8.8,2.3Hz, 1H)
13C NMR(101MHz,Chloroform-d)δ199.43,166.02,163.98,139.46,136.10,
131.17,128.48,127.33,113.54,108.50,103.59.
3c：Fusing point：145.3 DEG C, yellowish white powder, Rf=0.7 (petroleum ether:Ethyl acetate=3:1)
1H NMR (400MHz, Chloroform-d) δ 12.41 (s, 1H), 8.12-8.03 (m, 1H), 7.96 (dd, J=
8.0,1.0Hz, 1H), 7.52-7.48 (m, 1H), 7.32 (d, J=1.7Hz, 1H), 7.26-7.19 (m, 1H), 7.12 (d, J=
8.8Hz, 1H), 6.50 (d, J=2.4Hz, 1H), 6.35 (dd, J=8.8,2.4Hz, 1H)
13C NMR(101MHz,Chloroform-d)δ200.87,166.22,163.62,,139.57,136.15,
131.05,128.06,127.91,113.47,108.30,103.68.
3d：Fusing point：124 DEG C, white powder solid, Rf=0.6 (petroleum ether:Ethyl acetate=3:1)
1H NMR (400MHz, Chloroform-d) δ 12.72 (d, J=9.5Hz, 1H), 7.99-7.93 (m, 1H),
7.68 (d, J=2.0Hz, 1H), 7.66 (d, J=2.1Hz, 1H), 7.63 (dd, J=8.4,3.4Hz, 1H), 7.57 (dd, J=
12.8,8.8Hz, 2H), 6.53 (d, J=2.3Hz, 1H), 6.44 (ddd, J=8.6,6.2,2.4Hz, 1H), 3.05-2.94
(m,3H).
13C NMR(101MHz,Chloroform-d)δ202.88,174.19,165.07,163.22,162.11,
136.78,135.78,133.12,130.92,119.57,117.75,114.11,111.55,108.24,103.47.
3e：Fusing point：Brown oil, Rf=0.4 (petroleum ether:Ethyl acetate=3:1)
1H NMR (400MHz, Chloroform-d) δ 12.73 (d, J=18.5Hz, 1H), 8.06-7.96 (m, 1H),
7.70-7.39(m,4H),7.02-6.96(m,2H),6.56-6.40(m,2H).
13C NMR(101MHz,Chloroform-d)δ199.005,165.85,163.72,161.95,135.81,
135.20,131.42,130.49,115.32,114.11,113.13,107.85,103.62.
3f：Fusing point：61 DEG C, yellow solid, Rf=0.8 (petroleum ether:Ethyl acetate=3:1)
13C NMR(101MHz,Chloroform-d)δ201.607,165.39,137.39,135.52,133.50,
131.81,130.17,129.76,128.55,121.39,118.21,20.92。
Claims (5)
1. boron trifluoride is catalyzed the synthetic method of benzophenone compound, which is characterized in that include the following steps：
Substituted benzoic acid, resorcinol derivatives and catalyst boron trifluoride ether are added in reaction vessel, are gradually warming up to
It 95-120 DEG C, after reacting 10min-30min, is dissolved with ethyl acetate, saturated sodium bicarbonate washing, after dry, recrystallization, decoloration
Benzophenone compound is obtained, reaction formula is as follows：
2. the synthetic method of boron trifluoride catalysis benzophenone compound described in claim 1, which is characterized in that described
R in substituted benzoic acid1Including any one in hydrogen, bromine, iodine, hydroxyl, carboxyl, acetoxyl group, R1Substituting group position is not fixed,
Specifically include o-, m-, contraposition.
3. the synthetic method of boron trifluoride catalysis benzophenone compound described in claim 1, which is characterized in that described
R in resorcinol derivatives2Including hydroxyl, C1-C4Any one in alkyl, R2Substituting group position is not fixed, and is specifically included
O-, m-, contraposition.
4. the synthetic method of boron trifluoride catalysis benzophenone compound described in claim 1, which is characterized in that substituted benzene
The ratio between amount of substance of formic acid, resorcinol derivatives, catalyst is 1：0.8-2：0.1-0.8.
5. the synthetic method of boron trifluoride catalysis benzophenone compound described in claim 1, which is characterized in that substituted benzene
The ratio between amount of substance of formic acid, resorcinol derivatives, catalyst is 1：1：0.4.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039913A (en) * | 2018-10-15 | 2020-04-21 | 韦忠友 | Preparation method of compound with anti-tumor effect |
| CN113896703A (en) * | 2021-11-15 | 2022-01-07 | 西安久中生物科技有限公司 | Green preparation process of daidzein |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073407A (en) * | 2013-02-05 | 2013-05-01 | 芜湖市联合涂料有限责任公司 | Method for preparing 2, 4-dihydroxy benaophenonel by using indium trichloride to catalyze |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073407A (en) * | 2013-02-05 | 2013-05-01 | 芜湖市联合涂料有限责任公司 | Method for preparing 2, 4-dihydroxy benaophenonel by using indium trichloride to catalyze |
Non-Patent Citations (1)
| Title |
|---|
| SARVESH KUMAR ET AL: ""Arylakyl Ketones,Benzophenones,Desoxybenzoins and Chalcones Inhibit TNF-α Induced Expression of ICAM-1:Structure-Activity Analysis"", 《ARCH.PHARM.CHEM.LIFE.SCI》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039913A (en) * | 2018-10-15 | 2020-04-21 | 韦忠友 | Preparation method of compound with anti-tumor effect |
| CN113896703A (en) * | 2021-11-15 | 2022-01-07 | 西安久中生物科技有限公司 | Green preparation process of daidzein |
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