CN1817829A - Production of aryl-group-aryl biphenyl compound - Google Patents
Production of aryl-group-aryl biphenyl compound Download PDFInfo
- Publication number
- CN1817829A CN1817829A CN 200610049773 CN200610049773A CN1817829A CN 1817829 A CN1817829 A CN 1817829A CN 200610049773 CN200610049773 CN 200610049773 CN 200610049773 A CN200610049773 A CN 200610049773A CN 1817829 A CN1817829 A CN 1817829A
- Authority
- CN
- China
- Prior art keywords
- aryl
- preparation
- biphenyl compounds
- compounds according
- ome
- 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
- 239000004305 biphenyl Substances 0.000 title abstract description 5
- 235000010290 biphenyl Nutrition 0.000 title abstract description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title abstract description 5
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 46
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 aryl-aryl biphenyl compound Chemical class 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000004327 boric acid Substances 0.000 claims abstract description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 235000017550 sodium carbonate Nutrition 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 229940093916 potassium phosphate Drugs 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000000926 separation method Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000003444 phase transfer catalyst Substances 0.000 description 4
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PIMNFNXBTGPCIL-UHFFFAOYSA-N 1-(2-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=CC=C1Br PIMNFNXBTGPCIL-UHFFFAOYSA-N 0.000 description 1
- QBELEDRHMPMKHP-UHFFFAOYSA-N 1-bromo-2-chlorobenzene Chemical compound ClC1=CC=CC=C1Br QBELEDRHMPMKHP-UHFFFAOYSA-N 0.000 description 1
- JXMZUNPWVXQADG-UHFFFAOYSA-N 1-iodo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1I JXMZUNPWVXQADG-UHFFFAOYSA-N 0.000 description 1
- ZGQVZLSNEBEHFN-UHFFFAOYSA-N 2-(4-methylphenyl)benzonitrile Chemical group C1=CC(C)=CC=C1C1=CC=CC=C1C#N ZGQVZLSNEBEHFN-UHFFFAOYSA-N 0.000 description 1
- 241001504639 Alcedo atthis Species 0.000 description 1
- PMLRYPYQSAIBPM-UHFFFAOYSA-N C1=CC=CC=C1.[I].[Br] Chemical compound C1=CC=CC=C1.[I].[Br] PMLRYPYQSAIBPM-UHFFFAOYSA-N 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000000400 angiotensin II type 1 receptor blocker Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000037081 physical activity Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Production of aryl-aryl biphenyl compound is carried out by putting halogenated arene 1mmol, boric acid 1-2mmol, alkali 3-4mmol and palladium acetate0.25-2mmol into reactor, adding into organic solvent 3-4ml and water 1-9 ml, agitating at 25-36 degrees C for 0.5-2hrs, extracting by diethyl ether and drying to obtain the final product. Its advantages include short reaction time, more yields of product, gentle reaction condition and wider range of organic solvent and alkali.
Description
Technical field
The present invention relates to a kind of preparation method of aryl-aryl biphenyl compounds.
Background technology
The aryl-aryl biphenyl derivative is one of modal structure component in the natural product, has multiple important physical activity, and its purposes is extensively, at aspects such as medicine and agricultural chemicals huge value of exploiting and utilizing is arranged; Particularly 4-methyl-2 '-cyanobiphenyl, much treat hypertension especially with the key intermediate of sartans.
The Suzuki linked reaction is a kind of classic methods of preparation biphenyl compound, and its characteristics are to use aromatic halohydrocarbon and the phenylo boric acid generation biphenyl compound that reacts.How easy and synthetic efficiently this compounds?
Water is a kind of solvent of environmental protection, how to make organic reaction become the important topic that present people pay close attention in green solvent.Recently, it is found that when carrying out the Suzuki reaction in water when, the range of choice of substrate is subjected to certain restriction, when using some insoluble or solvability is bad substrates, reaction result is not very desirable (Bumagin, N.A.; Bykov, V.V.; Beletskaya, I.P.Bull.Acad.Sci.USSR, Div.Chem.Sci. (Engl.Transl.) 1989,38,2206).People added some phase-transfer catalysts or used some soluble parts to come this reaction of catalysis (Leadbeater, N.E. in water afterwards; Marco, M.J.Org.Chem.2003,68,5660.).Adopt organic solvent and water as cosolvent, overcome the solubility problem of substrate to a certain extent, and widened the range of choice of reaction substrate.Existing report uses ethanol (Jackson, W.R.; Marcuccio, S.M.; Naeslund, C.G.M.Chem.Commun.1994,2395.Deng, Y; Gong, L.; Mi, A.; Liu, H.; Jiang, Y.Synthesis 2003,337) and acetone (Goodson, F.E.; Wallow, T.I.; Novak, B.M.Org.Syntheses 1998,75,61.Wallow, T.I.; Novak, B.M.J.Org.Chem.1994,59; 5034.) as cosolvent; overcome the deliquescent problem of substrate, obtained gratifying achievement, still; in the process of concrete this reaction of enforcement; but need to take some measures, such as adding part or phase-transfer catalyst, the lengthening reaction times; make blanketing with inert gas etc., this has brought very big inconvenience for actual the use.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of aryl-aryl biphenyl compounds.
It is the halogenated aryl hydrocarbon with 1mmol, the boric acid of 1-2mmol, the alkali of 2-4mmol, the palladium of 0.25-2mol% adds the water of 3-4ml organic solvent and 1-9ml in reactor, stirred 0.5-2 hour down at 25-36 ℃, use extracted with diethyl ether, be spin-dried for solvent after, promptly get product.
Advantage of the present invention:
1) mixed solution of selecting water and organic solvent combines the advantage of single water solvent and single organic solvent as reaction solvent, reacts under the situation that does not have part and any phase-transfer catalyst, and yield is very high;
2) this reaction can well be carried out in air without any need for the protection of rare gas element;
3) this is reflected under the gentle condition and carries out, and the reaction times is short, the reaction yield height, and the simple ether kingfisher of process is got and just can reach separating of product and reaction system;
4) in this method, the range of choice of organic solvent and alkali is wide in range.
Embodiment
The present invention adopts organic solvent and water as cosolvent; in the presence of alkali effect and palladium, need not part and phase-transfer catalyst, need not the protection of rare gas element; halogenated aryl hydrocarbon and aryl boric acid generation cross-coupling reaction obtain various biphenyl compound.The equation that reacts basic is:
Described halogenated aryl hydrocarbon is R
1-Ph-X, boric acid are R
2PhB (OH)
2, wherein, when X is Br, R
1Be H, 4-CH
3, 4-NO
2, 4-OMe, 4-Cl, 4-COCH
3, 4-CN, 2-CH
3Or 3-OH, R
2Be H, 4-OMe or 4-CF
3When X=I, R
1Be 4-CH
3, 4-OMe or 4-NO
2, R
2Be H, 4-OMe or 4-CF
3Organic solvent is an ethanol, methyl alcohol, propyl alcohol, Virahol, acetone or N, dinethylformamide.The consumption of water is 2-9ml.Alkali is salt of wormwood, yellow soda ash, potassiumphosphate, potassium hydroxide or sodium hydroxide.Temperature of reaction is 25 ℃-35 ℃, and the reaction times is 0.5-1 hour.The consumption of palladium is 0.5-1.5%mol.
Following examples will help to understand the present invention, but be not limited to content of the present invention:
Embodiment 1
Take by weighing 1mmol to the methyl bromobenzene, the PhB of 2mmol (OH)
2, the yellow soda ash of 2mmol, the palladium of 0.25mol% adds the water of 3ml acetone and 1ml in the little flask of 25ml, stirred two hours down at 35 ℃.After reaction finishes, with the extracted with diethyl ether of 4*10ml.After being spin-dried for solvent, promptly get product, productive rate is 99%.Carry out the post separation with petrol ether/ethyl acetate and can obtain analytically pure sample.
1H?NMR(500MHz，CDCl
3，TMS)：δ7.58(d，2H，J＝7.5Hz)，7.49(d，2H，J＝8.0Hz)，7.43(t，2H，J＝7.5Hz)，7.32(t，1H，J＝7.3Hz)，7.25(d，2H，J＝7.5Hz).MS(EI)：m/z(％)：168(100)[M
+]，167(68)，165(22)，152(20)，115(6).
Embodiment 2
Take by weighing 1mmol to methoxyl group iodine (bromine) benzene, the PhB of 1.5mmol (OH)
2, the yellow soda ash of 2mmol, the palladium of 0.5mol% adds the water of 3ml acetone and 3.5ml in the little flask of 25ml, stirred one hour down at 35 ℃.After reaction finishes, with the extracted with diethyl ether of 4*10ml.After being spin-dried for solvent, promptly get product, productive rate is 98%.Carry out the post separation with petrol ether/ethyl acetate and can obtain analytically pure sample.
Embodiment 3
Take by weighing 1mmol to the nitro iodobenzene, the PhB of 1.5mmol (OH)
2, the yellow soda ash of 2mmol, the palladium of 0.5mol% adds the water of 3ml acetone and 3.5ml in the little flask of 25ml, stir a half an hour down at 25 ℃.After reaction finishes, with the extracted with diethyl ether of 4*10ml.After being spin-dried for solvent, promptly get product, productive rate is 90%.Carry out the post separation with petrol ether/ethyl acetate and can obtain analytically pure sample.
1H?NMR(500MHz，CDCl
3，TMS)：δ8.32(d，2H，J＝9.0Hz)，7.75(d，2H，J＝9.0Hz)，7.64(d，2H，J＝7.0Hz)，7.51(t，2H，J＝7.5Hz)，7.46(t，1H，J＝7.2Hz).MS(EI)：m/z(％)：199(100)[M
+]，169(37)，152(100)，141(24)，115(13)，76(13)，63(7)，51(6).
Embodiment 4
Take by weighing the para chlorobromobenzene of 1mmol, the PhB of 1mmol (OH)
2, the yellow soda ash of 2mmol, the palladium of 0.5mol% adds the water of 3ml acetone and 3.5ml in the little flask of 25ml, stirred one hour down at 35 ℃.After reaction finishes, with the extracted with diethyl ether of 4*10ml.After being spin-dried for solvent, promptly get product, productive rate is 99%.Carry out the post separation with petrol ether/ethyl acetate and can obtain analytically pure sample.
Embodiment 5
Take by weighing 1mmol to the ethanoyl bromobenzene, the PhB of 1.5mmol (OH)
2, the yellow soda ash of 2mmol, the palladium of 0.5mol% adds the water of 3ml acetone and 3.5ml in the little flask of 25ml, stir half hour down at 35 ℃.After reaction finishes, with the extracted with diethyl ether of 4*10ml.After being spin-dried for solvent, promptly get product, productive rate is 99%.Carry out the post separation with petrol ether/ethyl acetate and can obtain analytically pure sample.
1H?NMR(500MHz，CDCl
3，TMS)：δ8.03(d，2H，J＝8.4Hz)，7.69(d，2H，J＝4.0Hz)，7.63(t，2H，J＝4.5Hz)，7.48(t，2H，J＝7.5Hz)，7.40(t，1H，J＝7.0Hz)，2.64(s，3H).MS(EI)：m/z(％)：196(51)[M
+]，181(100)，153(33)，152(51)，76(13)，43(4).
Embodiment 6
Take by weighing 1mmol to the methyl bromobenzene, the 4-CF of 2mmol
3PhB (OH)
2, the yellow soda ash of 4mmol, the palladium of 2mol% adds the water of 3ml acetone and 3.5ml in the little flask of 25ml, stirred one hour down at 35 ℃.After reaction finishes, with the extracted with diethyl ether of 4*10ml.After being spin-dried for solvent, promptly get product, productive rate is 86%.Carry out the post separation with petrol ether/ethyl acetate and can obtain analytically pure sample.
Embodiment 7
Take by weighing 1mmol to the methyl bromobenzene, the 4-OMePhB of 2mmol (OH)
2, the yellow soda ash of 4mmol, the palladium of 2mol% adds the water of 4ml acetone and 9ml in the little flask of 25ml, stir half hour down at 36 ℃.After reaction finishes, with the extracted with diethyl ether of 4*10ml.After being spin-dried for solvent, promptly get product, productive rate is 98%.Carry out the post separation with petrol ether/ethyl acetate and can obtain analytically pure sample.
Claims (7)
1. the preparation method of an aryl-aryl biphenyl compounds, it is characterized in that: the halogenated aryl hydrocarbon of 1mmol, the boric acid of 1-2mmol, the alkali of 2-4mmol, the palladium of 0.25-2mol% add the water of 3-4ml organic solvent and 1-9ml in reactor, stirred 0.5-2 hour down at 25-36 ℃, use extracted with diethyl ether, be spin-dried for solvent after, promptly get product.
2. the preparation method of a kind of aryl-aryl biphenyl compounds according to claim 1, it is characterized in that: described halogenated aryl hydrocarbon is R
1-Ph-X, boric acid are R
2PhB (OH)
2, wherein, when X is Br, R
1Be H, 4-CH
3, 4-NO
2, 4-OMe, 4-Cl, 4-COCH
3, 4-CN, 2-CH
3Or 3-OH, R
2Be H, 4-OMe or 4-CF
3When X=I, R
1Be 4-CH
3, 4-OMe or 4-NO
2, R
2Be H, 4-OMe or 4-CF
3
3. the preparation method of a kind of aryl-aryl biphenyl compounds according to claim 1, it is characterized in that: described organic solvent is an ethanol, methyl alcohol, propyl alcohol, Virahol, acetone or N, dinethylformamide.
4. the preparation method of a kind of aryl-aryl biphenyl compounds according to claim 1, it is characterized in that: the consumption of described water is 2-9ml.
5. the preparation method of a kind of aryl-aryl biphenyl compounds according to claim 1, it is characterized in that: described alkali is salt of wormwood, yellow soda ash, potassiumphosphate, potassium hydroxide or sodium hydroxide.
6. the preparation method of a kind of aryl-aryl biphenyl compounds according to claim 1, it is characterized in that: described temperature of reaction is 25 ℃-35 ℃, and the reaction times is 0.5-1 hour.
7. the preparation method of a kind of aryl-aryl biphenyl compounds according to claim 1, it is characterized in that: the consumption of described palladium is 0.5-1.5%mol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100497734A CN100491312C (en) | 2006-03-10 | 2006-03-10 | Production of aryl-group-aryl biphenyl compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100497734A CN100491312C (en) | 2006-03-10 | 2006-03-10 | Production of aryl-group-aryl biphenyl compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1817829A true CN1817829A (en) | 2006-08-16 |
| CN100491312C CN100491312C (en) | 2009-05-27 |
Family
ID=36918067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100497734A Expired - Fee Related CN100491312C (en) | 2006-03-10 | 2006-03-10 | Production of aryl-group-aryl biphenyl compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100491312C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100519490C (en) * | 2007-05-23 | 2009-07-29 | 浙江工业大学 | Synthesis method for biphenyl compound |
| CN102381917A (en) * | 2011-08-11 | 2012-03-21 | 浙江中欣化工股份有限公司 | Preparation method of biphenyl compound |
| CN103864567A (en) * | 2014-03-07 | 2014-06-18 | 山东大学 | Method for preparing coupled arene compound |
| CN111039796A (en) * | 2019-12-12 | 2020-04-21 | 德州学院 | Novel synthesis method of 4' -chloro-2-aminobiphenyl |
-
2006
- 2006-03-10 CN CNB2006100497734A patent/CN100491312C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100519490C (en) * | 2007-05-23 | 2009-07-29 | 浙江工业大学 | Synthesis method for biphenyl compound |
| CN102381917A (en) * | 2011-08-11 | 2012-03-21 | 浙江中欣化工股份有限公司 | Preparation method of biphenyl compound |
| CN102381917B (en) * | 2011-08-11 | 2013-11-06 | 浙江中欣化工股份有限公司 | Preparation method of biphenyl compound |
| CN103864567A (en) * | 2014-03-07 | 2014-06-18 | 山东大学 | Method for preparing coupled arene compound |
| CN103864567B (en) * | 2014-03-07 | 2015-11-25 | 山东大学 | A kind of preparation method of biaryl compound |
| CN111039796A (en) * | 2019-12-12 | 2020-04-21 | 德州学院 | Novel synthesis method of 4' -chloro-2-aminobiphenyl |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100491312C (en) | 2009-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1817829A (en) | Production of aryl-group-aryl biphenyl compound | |
| CN103242216A (en) | Synthesis method of N-Boc-hexahydro-5-oxo-cyclopenta (C) pyrrole | |
| CN1995272A (en) | Superbranched luminous high polymer and its preparation method and application | |
| CN101289439A (en) | Process for preparing arabglycal | |
| CN1304360C (en) | Preparation method of N,N-dimethyl-3-hydroxy-3-aryl propyl amine | |
| CN114315532B (en) | Method for synthesizing 1, 4-tetraalkoxy-2-butene from 2, 2-dialkoxy acetaldehyde | |
| CN101050225A (en) | New method for synthesizing 2 - L - ribose from 2 - D - ribose | |
| CN1263729C (en) | Process for preparing 3,4-diaminodiphenyl ether | |
| CN1837193A (en) | Process for preparing diindolylmethane derivatives | |
| CN110156581A (en) | A kind of method of one step photocatalysis lignin depolymerization and amination synthesis nitrogenous aromatic compound | |
| CN104311432B (en) | ADZ6140 important intermediate (1R, 2S)-2-(3,4-difluoro-benzene base) preparation method of cyclopropylamine | |
| CN1824646A (en) | Aryl or aryl amine substuted quinone kind compound and its preparation method | |
| CN103553934A (en) | N-isopropyl-4-fluoroaniline preparation method | |
| CN1539805A (en) | Method for synthesizing pterostilbene | |
| CN102381917A (en) | Preparation method of biphenyl compound | |
| CN1903813A (en) | Preparation method of 3,5-difluoro biphenyl derivative | |
| CN104892336B (en) | A kind of preparation method of secondary-amine compound | |
| CN100522899C (en) | Method for preparing symmetrical benzocyclobutene compound | |
| CN1594333A (en) | Process for synthesizing liquid crystal compound by catalytic cross-coupling of diphenyl-phosphino- palladium acetate | |
| CN109422634A (en) | A kind of synthetic method of 3- carbonyl indanone compounds | |
| CN1631868A (en) | Process for preparing multi-fluorine-substituted terallethrin compound | |
| CN111362796B (en) | Method for reducing and hydrogenating tertiary alkyl alcohol | |
| CN1293037C (en) | Process for preparing terbinafine hydrochliride | |
| CN1228448C (en) | Process for preparing chiral medicine intermediate (R)-2-halogen-1-(substituted phenyl) ethanol | |
| CN1207258C (en) | Process for synthesizing 2,15-hexadecyl diketone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090527 Termination date: 20110310 |