CN1368500A - Process for preparing unsymmetric phenylpyridyl substances - Google Patents
Process for preparing unsymmetric phenylpyridyl substances Download PDFInfo
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- CN1368500A CN1368500A CN 01103688 CN01103688A CN1368500A CN 1368500 A CN1368500 A CN 1368500A CN 01103688 CN01103688 CN 01103688 CN 01103688 A CN01103688 A CN 01103688A CN 1368500 A CN1368500 A CN 1368500A
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- Prior art keywords
- aminopyridine
- synthetic method
- reaction
- asymmetric pyridine
- carbon monoxide
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- 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.)
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- -1 phenylpyridyl Chemical group 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000000126 substance Substances 0.000 title description 2
- 235000013877 carbamide Nutrition 0.000 claims abstract description 19
- 238000010189 synthetic method Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 10
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 10
- 150000003927 aminopyridines Chemical class 0.000 claims abstract description 8
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 6
- 239000011669 selenium Substances 0.000 claims abstract description 6
- 239000012442 inert solvent Substances 0.000 claims abstract description 5
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 claims description 8
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005810 carbonylation reaction Methods 0.000 claims description 3
- 229960004979 fampridine Drugs 0.000 claims description 3
- IXDBNSMHWQNXQO-UHFFFAOYSA-N 1-phenyl-1-pyridin-2-ylurea Chemical compound C=1C=CC=NC=1N(C(=O)N)C1=CC=CC=C1 IXDBNSMHWQNXQO-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 150000005181 nitrobenzenes Chemical class 0.000 claims 1
- 239000005648 plant growth regulator Substances 0.000 abstract description 4
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 231100000086 high toxicity Toxicity 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- GAOJUAYPDKVFDO-UHFFFAOYSA-N pyridine;urea Chemical compound NC(N)=O.C1=CC=NC=C1 GAOJUAYPDKVFDO-UHFFFAOYSA-N 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 3
- YQYGPGKTNQNXMH-UHFFFAOYSA-N 4-nitroacetophenone Chemical compound CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YQYGPGKTNQNXMH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical class NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 1
- WZYOSMAXXLCTGP-UHFFFAOYSA-N 1-phenyl-3-pyridin-4-ylurea Chemical compound C=1C=NC=CC=1NC(=O)NC1=CC=CC=C1 WZYOSMAXXLCTGP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008430 aromatic amides Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000105 evaporative light scattering detection Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- GPXLRLUVLMHHIK-UHFFFAOYSA-N forchlorfenuron Chemical compound C1=NC(Cl)=CC(NC(=O)NC=2C=CC=CC=2)=C1 GPXLRLUVLMHHIK-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- CPGRMGOILBSUQC-UHFFFAOYSA-N phosphoryl azide Chemical compound [N-]=[N+]=NP(=O)(N=[N+]=[N-])N=[N+]=[N-] CPGRMGOILBSUQC-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
Abstract
一种非对称吡啶脲类的合成方法,是采用硒或二氧化硒做催化剂,三级胺做助催化剂,按1∶1mol的比例将硝基化合物与氨基吡啶溶于盛有惰性溶剂的高压釜中,密封,充入一氧化碳气体,放入油浴中,迅速升温至100℃－170℃,保温下反应1－5小时,完毕,冷却,放掉残气,经过滤、干燥、重结晶等产品。本该方法不仅操作简单,成本较低,而且产品收率较高,纯度较好,所合成的非对称吡啶脲类可作高低毒的植物生长调节剂。A kind of synthetic method of unsymmetrical pyridine urea, is to use selenium or selenium dioxide as catalyst, tertiary amine as cocatalyst, dissolve nitro compound and aminopyridine in the autoclave filled with inert solvent according to the ratio of 1:1mol Medium, sealed, filled with carbon monoxide gas, placed in an oil bath, rapidly heated to 100°C-170°C, and reacted for 1-5 hours under heat preservation, after completion, cooled, let off residual gas, filtered, dried, recrystallized and other products . The method not only has simple operation and low cost, but also has high product yield and good purity, and the synthesized asymmetric pyridine ureas can be used as high and low toxicity plant growth regulators.
Description
The selenium that the present invention relates to nitro-compound and aminopyridines helps carbonylation reaction to prepare the method for asymmetrical phenylpyridyl ureas plant-growth regulator.
Asymmetric phenylpyridyl ureas material is a kind of phenylurea class phytokinin material (phytokinin is a kind of hormone of plant-growth) with higher physiologically active.But coordinate plant growth, precocity, the aging that delays crop leaf, increase crop yield are the plant-growth regulator of a class high-efficiency low-toxicity.What commercially produced at present mainly is: N-phenyl-N '-(4-pyridyl) urea, N-phenyl-N '-(2-chloro-4-pyridyl) urea etc.
Mainly containing of the synthetic method bibliographical information of phenylpyridyl ureas material is following several:
1. isocyanic ester method.The substituted urea class material is to adopt amine and isocyanic ester one step condensation to make traditionally, but this method is used and is generated a large amount of chlorine byproducts in hypertoxic phosgene and the reaction process, cause equipment to be subjected to heavy corrosion, cause the trouble on the manipulation: isocyanic ester is active especially simultaneously, and easy and air reacts, so high especially AlexandreHocquet of technical requirement to testing, Jacques Tohier, J.of Chem.Educ., 1994,71 (12), 1092-1094; And L.V.Sudha, D.N.Sathyanarayana, J.of Molecular.Struc., 1985,131,141-146).
2. general trinitride method.20 beginning of the century Curtius propose by the different reaction conditions of control, can prepare fragrance or assorted aromatic amides and ureas material (B.Stanovnik, M.Tister with trinitride, V-Golob, I.Hvala, O.Nikoliv, J.Heterocyclic Chem.1980,17,733-6)
3. phosphoryl azide thing method.Make reagent with phenyl-N '-phenyl phosphoryl azide thing, aromatic acid and fragrant primary amine react in acetonitrile solution and generate aryl urea material (Ana Arrieta, ClaudioPalomo, Tetrahedron Lett.1981,22 (18), 1729-1732; With Arrieta Ana, PalomoClaudio, Bull.Soc.Chim.Fr.1982, (1-2; Pt.27), 7-11).
The method that more than prepares phenylpyridyl ureas material; all used the isocyanates material directly or indirectly; isocyanic ester not only toxicity is big; environmental pollution is serious; and be difficult for storage; easily react,, experimental technique and equipment are all had relatively high expectations so reaction generally will be carried out under anhydrous, anaerobic, nitrogen protection with airborne water, oxygen.
The object of the present invention is to provide a kind of method of more simple and easy to do synthesis of phenyl pyridyl urea, this method productive rate is higher, and quality product is more stable, and aftertreatment is easier to.
The invention provides a kind of synthetic method of asymmetric pyridine ureas plant-growth regulator, it is characterized in that: the carbonylation reaction that under selenium or tin anhydride catalysis, carries out carbon monoxide with nitro-compound and aminopyridine, reaction is to carry out in enclosed autoclave, adopt inert solvent, reaction pressure is that 0.1-4.0MPa reacts under 100-170 ℃ of temperature, and the feed ratio of nitro-compound and aminopyridines material is 1: 1mol.
In the synthetic method of above-mentioned asymmetric pyridine ureas, it is characterized in that: nitro-compound is to have the various nitrobenzene matters of giving electronics or electron-withdrawing substituent, and the aminopyridines material is 2-aminopyridine, 3-aminopyridine or 4-aminopyridine.
In the synthetic method of above-mentioned asymmetric pyridine ureas, it is characterized in that: also adopt tertiary amine to do promotor, carbon monoxide is made reductive agent.
Synthetic method at above-mentioned asymmetric pyridine ureas is characterized in that: catalyst levels is the 1-5% of nitro-compound weight, and the tertiary amine consumption is a chemical dose.
Synthetic method at above-mentioned asymmetric pyridine ureas is characterized in that: inert solvent can be toluene, acetone or tetrahydrofuran (THF).
In addition, the synthetic method at above-mentioned asymmetric pyridine ureas is characterized in that: reacting coarse product adopts methyl alcohol, ethanol or sherwood oil etc. to carry out recrystallization.Find in the experiment that selenium is made catalyzer, triethylamine is made catalyzer, and toluene is made solvent, reacts 4h under 150 ℃ of temperature, and the product yield that obtains is higher, and purity is better.The equation of reaction is:
In the formula, R is various electronics or the electrophilic substituting groups given.
The present invention has used selenium or tin anhydride to make catalyzer, and the reaction times is shorter, and reaction yield and selectivity are better, and the aftertreatment ratio of product is easier to, and production technique is simple, and operation is easily gone.
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
In 100 milliliters stainless steel autoclave, add 0.94g 2-aminopyridine, 1.23g oil of mirbane, 0.0395g selenium powder, 1.5ml triethylamine and 10g toluene, sealing charges into carbon monoxide 1.0MPa, puts into oil bath, be warming up to 100 ℃ rapidly, insulation is reaction 4h down, is cooled to room temperature, opens still, the solid of gained and the solid merging that mother liquor concentrates gained will be filtered, drying is weighed to such an extent that product purity is 85%, and yield is 61.5%.Assay adopts highly effective liquid phase chromatographic system, do moving phase with methyl alcohol, tetrahydrofuran (THF), water, flow velocity 0.8ml/min, (DIDL 10 μ l 250 * 4mm) are chromatographic column with LiChrosorb, with ELSD is detector, and 70 ℃ of drift tube temperatures, gas flow are 1.605LPM, sample size is 2 μ l, and the peak area external standard method is quantitative.
Embodiment 2
In 100 milliliters stainless steel autoclave, add 0.94g 2-aminopyridine, 1.65g 4-nitro-acetophenone, 0.0395g selenium powder, 1.5ml triethylamine and 10g toluene, sealing, charge into carbon monoxide 3.0MPa, put into oil bath and be warming up to 150 ℃ rapidly, heating 4h, after being cooled to room temperature, open still, will filter the solid of gained and the solid merging that mother liquor concentrates gained, drying, weigh to such an extent that product purity is 92.9%, yield is 70.8%.
Embodiment 3
In 100 milliliters stainless steel autoclave, add 0.94g 3-aminopyridine, 1.74g 4-oil of mirbane, 0.0395g selenium powder, 1.5ml triethylamine and 10g toluene, sealing, charge into carbon monoxide 3.0MPa, put into oil bath and be warming up to 150 ℃ rapidly, heating 4h, after being cooled to room temperature, open still, will filter the solid of gained and the solid merging that mother liquor concentrates gained, drying, weigh product purity nearly 100%, yield is 77.5%.
Embodiment 4
In 100 milliliters stainless steel autoclave, add 0.94g 3-aminopyridine, 1.65g 4-nitro-acetophenone, 0.0395g selenium powder, 1.5ml triethylamine and 10g toluene, sealing charges into carbon monoxide 4.0MPa, puts into oil bath and is warming up to 150 ℃ rapidly, heating 4h, after being cooled to room temperature, open still, will filter the solid of gained and the solid merging that mother liquor concentrates gained, carry out recrystallization with sherwood oil, dry recrystallized product, weigh product purity nearly 100%, yield is 88.6%.
Embodiment 5
In 100 milliliters stainless steel autoclave, add 0.94g 4-aminopyridine, 1.37g 4-N-methyl-p-nitroaniline, 0.0395g selenium powder, 1.5ml triethylamine and 10g toluene, sealing, charge into carbon monoxide 2.0MPa, put into oil bath and be warming up to 150 ℃ rapidly, heating 4h, after being cooled to room temperature, open still, will filter the solid of gained and the solid merging that mother liquor concentrates gained, drying, weigh to such an extent that product purity is 87.2%, yield is 80.7%.
By the result of the foregoing description as can be known, the method reaction times of the present invention is shorter, and reaction yield and selectivity are better, and the aftertreatment ratio of product is easier to, and production technique is simple, and operation is easily gone.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011036885A CN1156450C (en) | 2001-02-09 | 2001-02-09 | A kind of preparation method of unsymmetrical phenylpyridyl urea |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011036885A CN1156450C (en) | 2001-02-09 | 2001-02-09 | A kind of preparation method of unsymmetrical phenylpyridyl urea |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1368500A true CN1368500A (en) | 2002-09-11 |
| CN1156450C CN1156450C (en) | 2004-07-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011036885A Expired - Fee Related CN1156450C (en) | 2001-02-09 | 2001-02-09 | A kind of preparation method of unsymmetrical phenylpyridyl urea |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312119C (en) * | 2004-04-29 | 2007-04-25 | 中国科学院大连化学物理研究所 | Process for synthesizing aryl substituted N-aryl amide compounds |
| CN1323075C (en) * | 2003-12-11 | 2007-06-27 | 中国科学院大连化学物理研究所 | A method for synthesizing N-pyridylbenzamide derivatives |
-
2001
- 2001-02-09 CN CNB011036885A patent/CN1156450C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323075C (en) * | 2003-12-11 | 2007-06-27 | 中国科学院大连化学物理研究所 | A method for synthesizing N-pyridylbenzamide derivatives |
| CN1312119C (en) * | 2004-04-29 | 2007-04-25 | 中国科学院大连化学物理研究所 | Process for synthesizing aryl substituted N-aryl amide compounds |
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| Publication number | Publication date |
|---|---|
| CN1156450C (en) | 2004-07-07 |
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