CN1215717A - Process for synthesis of aryl alpha-acyl aryl ketone compound - Google Patents
Process for synthesis of aryl alpha-acyl aryl ketone compound Download PDFInfo
- Publication number
- CN1215717A CN1215717A CN97107171.3A CN97107171A CN1215717A CN 1215717 A CN1215717 A CN 1215717A CN 97107171 A CN97107171 A CN 97107171A CN 1215717 A CN1215717 A CN 1215717A
- Authority
- CN
- China
- Prior art keywords
- aryl
- ketone compound
- acyl
- alpha
- aryl ketone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 title description 9
- 230000015572 biosynthetic process Effects 0.000 title description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- MWKAGZWJHCTVJY-UHFFFAOYSA-N 3-hydroxyoctadecan-2-one Chemical compound CCCCCCCCCCCCCCCC(O)C(C)=O MWKAGZWJHCTVJY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- -1 phenyl aldehyde Chemical class 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for synthesizing aryl alpha-acyl aryl ketone compound features the solid-phase oxidizing reaction of arylacryloin in the presence of FeCl3 in the condition of no solvent. Its advantages are simple method, low cost and no environmental pollution.
Description
The present invention relates to the method for fragrant acyloin oxidation synthesis of aryl alpha-acyl aryl ketone compound.
Japan succeeds in developing benzil from early seventies
As the photosensitizers of ultraviolet curable resin (UV resin) and since making it to drop into suitability for industrialized production, owing to adapted in coating and the requirement with an organic solvent of printing-ink domain restrictions, the demand of aromatic diacyl is growing, and its Application Areas also constantly enlarges.Aromatic diacyl (benzil and replacement benzil) has been organic synthesis, agrochemicals and medical synthetic important intermediate.
The synthetic of aryl alpha-acyl aryl ketone compound generally gets fragrant accordingly acyloin with aromatic aldehyde (phenyl aldehyde or substituted benzaldehyde) with the NaCN condensation at present
, make aryl alpha-acyl aryl ketone compound through nitric acid oxidation again.Cause public hazards owing to producing nitrous acid gas in the reaction process, and reaction is violent, is difficult to control.Though also there is report to come the acyloin of oxidation virtue to prepare corresponding aryl alpha-acyl aryl ketone compound with some gentle oxygenants, not severe reaction conditions often, be exactly reaction reagent costliness, preparation difficulty, even the generation serious environmental polluted.
At present getting aryl alpha-acyl aryl ketone compound from fragrant acyloin oxidation all carries out solution.The toxicity of organic solvent and easy volatile cause serious pollution to human environment.The cry that environment and health requirements reduce with an organic solvent is more and more stronger.
The purpose of this invention is to provide a kind of solvent that do not use, less contamination use cheap oxygenant, easily with the method for fragrant acyloin oxidation synthesis of aryl alpha-acyl aryl ketone compound.
Technical scheme of the present invention is as follows:
A kind of synthesizing has
The method of the aryl alpha-acyl aryl ketone compound of structure, it is with corresponding fragrant acyloin (ArCH-CAr, Ar are aryl) porphyrize, adds FeCl
3Or FeCl
3Crystalline hydrate, porphyrize together again, reacting by heating promptly makes aryl alpha-acyl aryl ketone compound.Wherein Ar-can be ph-, p-C1-ph-, p-CH
3O-ph-, or p-CH
3Groups such as-ph-.
The structure of Ar is as follows: a.ph-; B.p-Cl-ph-; C.p-CH
3O-ph-; D.p-CH
3-ph-. reaction can be carried out between 70-100 ℃, and preferred temperature is 80-90 ℃, the temperature of reaction that raises certainly, only otherwise reactant or product are decomposed all to be allowed.The general 3-4 of reacting by heating hour, promptly obtain the reaction product aryl alpha-acyl aryl ketone compound, wash the raw product that de-iron salt promptly gets aryl alpha-acyl aryl ketone compound with water, promptly get the highly finished product of aromatic diacyl again through recrystallization, productive rate reaches more than 90%.
The method of synthesis of aryl alpha-acyl aryl ketone compound of the present invention does not need any solvent, reaction conditions gentleness, easy to operate, safety, oxygenant FeCl
3Or FeCl
3Crystalline hydrate inexpensive.Therefore method of the present invention be a kind of pollution-free, prepare the method for aromatic diacyl by fragrant acyloin cheaply.
Further specify method of the present invention by the following examples.
Embodiment:
Take by weighing 2.123g (0.01mol) bitter almond oil camphor (1a) porphyrize in agate mortar, power adds the FeCl of 0.03mol then
36H
2O, porphyrize is transferred to mixture in the reaction tubes, reacts 4h in 90 ℃ thermostatic bath.After being cooled to room temperature, add 40mL H
2O, thorough washing, suction filtration is used the H of 10mL * 4 again
2O washes, and gets faint yellow crude product 2.02g, and m.p.91-93 ℃, use 5mL 95% ethyl alcohol recrystallization again, get faint yellow needle crystal thing (2a) 1.998g, m.p.93-94.5 ℃ (literature value: 92-94 ℃), productive rate 95%.
Compound 2 (b-d) is synthesized by above-mentioned similar approach, and temperature of reaction is 80 ℃, and the reaction times is 4h, and other data see Table 1.
The physical constant of compound 2 (a-d), productive rate, ultimate analysis data see Table 1, IR,
1The HNMR data see Table 2.
Table 1 compound 2 (synthesis condition, fusing point, productive rate and the ultimate analysis data of a～d)
| Compound | Molecular formula | Synthesis temperature/℃ | Fusing point (literature value)/℃ | Productive rate/% | Ultimate analysis (calculated value)/% |
| ?C?????????????H | |||||
| 2a | ?C 14H 10O 2 | ????90 | 93～94.5(92～94) (1) | 95.0 | ?80.29(79.99)??4.71(4.79) |
| 2b | ?C 14H 8Cl 2O 2 | ????80 | 196～197(195～196) (2) | 94.0 | ?60.34(60.24)??3.49(2.89) |
| 2c | ?C 16H 14O 4 | ????80 | 133～134(131～133) (1) | 89.5 | ?71.69(71.10)??5.10(5.22) |
| 2d | ?C 16H 14O 2 | ????80 | 102～104(103～104) (1) | 93.0 | ?80.31(80.65)??5.49(5.92) |
*Reaction times is 4 hours,
(1)Ho,T.L.,Synthesis,1972:697
(2)Gomberg,M.,Van?Natta,F.J.,J.Am.Chem.Soc.,1929,51:2241
Table 2 compound 2 (IR of a～d) and
1The HNMR data
| Compound | ????IR,U max/cm -1 | ???? 1HNMR,δ/ppm |
| ????2a | 1658,1592,1578,794,717,696,681 | ?7.16～8.10(10H,m,Ar-H) |
| ????2b | 1661,1586,880,834,734 | ?7.45,7.80(8H,dd,Ar-H) |
| ????2c | 1659,1597,1510,799,830 | ?3.85(6H,s,2CH 3),6.85,7.85 (8H,dd,Ar-H) |
| ????2d | 1660,1595,1570,1450,875,830,780 ,740 | 2.41(6H,s,2CH 3),7.25,7.80 (8H,dd,Ar-H) |
Claims (5)
1. a synthetic method with aryl alpha-acyl aryl ketone compound of Arc-cAr structure is characterized in that corresponding fragrant acyloin porphyrize, adds FeCl
3(or FeCl
3Crystalline hydrate), porphyrize together again, reacting by heating promptly makes aryl alpha-acyl aryl ketone compound.
2. the method for making of aryl alpha-acyl aryl ketone compound according to claim 1 is characterized in that Ar-is ph-, p-Cl-ph-, p-CH
3O-ph-, or p-CH
3-ph-group.
3. the method for making of aryl alpha-acyl aryl ketone compound according to claim 1 is characterized in that reacting by heating is in reaction more than 70 ℃.
4. the method for making of aryl alpha-acyl aryl ketone compound according to claim 1 is characterized in that reacting by heating 3-4 hour.
5. the method for making of aryl alpha-acyl aryl ketone compound according to claim 1 is characterized in that making aryl alpha-acyl aryl ketone compound after washing promptly gets the raw product of aryl alpha-acyl aryl ketone compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97107171A CN1099404C (en) | 1997-10-29 | 1997-10-29 | Process for synthesis of aryl alpha-acyl aryl ketone compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97107171A CN1099404C (en) | 1997-10-29 | 1997-10-29 | Process for synthesis of aryl alpha-acyl aryl ketone compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1215717A true CN1215717A (en) | 1999-05-05 |
| CN1099404C CN1099404C (en) | 2003-01-22 |
Family
ID=5169348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97107171A Expired - Fee Related CN1099404C (en) | 1997-10-29 | 1997-10-29 | Process for synthesis of aryl alpha-acyl aryl ketone compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1099404C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332923C (en) * | 2005-11-16 | 2007-08-22 | 陕西师范大学 | 2-(9-anthryl)-2-carbonylethyl acetate solid phase synthesis method |
| CN109456271A (en) * | 2018-11-20 | 2019-03-12 | 宁波职业技术学院 | A kind of synthetic method of dilantin sodium |
| CN111978258A (en) * | 2020-08-13 | 2020-11-24 | 山西新宝源制药有限公司 | Method for preparing phenytoin sodium |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD144759B1 (en) * | 1979-07-10 | 1983-01-26 | Peter Palitzsch | METHOD FOR PRODUCING BENZIL |
-
1997
- 1997-10-29 CN CN97107171A patent/CN1099404C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332923C (en) * | 2005-11-16 | 2007-08-22 | 陕西师范大学 | 2-(9-anthryl)-2-carbonylethyl acetate solid phase synthesis method |
| CN109456271A (en) * | 2018-11-20 | 2019-03-12 | 宁波职业技术学院 | A kind of synthetic method of dilantin sodium |
| CN109456271B (en) * | 2018-11-20 | 2022-06-21 | 宁波职业技术学院 | Synthesis method of phenytoin sodium |
| CN111978258A (en) * | 2020-08-13 | 2020-11-24 | 山西新宝源制药有限公司 | Method for preparing phenytoin sodium |
| CN111978258B (en) * | 2020-08-13 | 2021-05-25 | 山西新宝源制药有限公司 | Method for preparing phenytoin sodium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1099404C (en) | 2003-01-22 |
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| C14 | Grant of patent or utility model | ||
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