CN108586286A - A kind of method that the amidine compound degradation of rare earth catalyst generates nitrile and amine - Google Patents
A kind of method that the amidine compound degradation of rare earth catalyst generates nitrile and amine Download PDFInfo
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- CN108586286A CN108586286A CN201810484744.3A CN201810484744A CN108586286A CN 108586286 A CN108586286 A CN 108586286A CN 201810484744 A CN201810484744 A CN 201810484744A CN 108586286 A CN108586286 A CN 108586286A
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- 238000006731 degradation reaction Methods 0.000 title claims abstract description 23
- 230000015556 catabolic process Effects 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 17
- 150000001412 amines Chemical class 0.000 title claims abstract description 14
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 13
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 13
- -1 amidine compound Chemical class 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 150000001409 amidines Chemical class 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 150000002431 hydrogen Chemical group 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 30
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 9
- NWPNXBQSRGKSJB-UHFFFAOYSA-N 2-methylbenzonitrile Chemical compound CC1=CC=CC=C1C#N NWPNXBQSRGKSJB-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- AQSJLSKJCSBFNY-UHFFFAOYSA-N N-methyl-N-phenylthiophene-2-carboximidamide Chemical class CN(C1=CC=CC=C1)C(=N)C2=CC=CS2 AQSJLSKJCSBFNY-UHFFFAOYSA-N 0.000 description 2
- LQFLWKPCQITJIH-UHFFFAOYSA-N n-allyl-aniline Chemical compound C=CCNC1=CC=CC=C1 LQFLWKPCQITJIH-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- GJNGXPDXRVXSEH-UHFFFAOYSA-N 4-chlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1 GJNGXPDXRVXSEH-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 210000000720 eyelash Anatomy 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to chemical technology field, the method for amidine compound degradation the generation nitrile and amine of specially a kind of rare earth catalyst.The present invention is that amidine compound is directly degraded and generates corresponding nitrile and amine under rare-earth catalysis system.The method of the present invention is applied widely, easy to operate and can generate nitrile in high yield in a mild condition, the high selectivity of reaction.
Description
Technical field
The invention belongs to chemical technology fields, and in particular to a kind of the amidine analog derivative degradation generation nitrile and amine of rare earth catalyst
Method.
Background technology
Amidine structural unit is widely present in pesticide original medicine, and residue increasingly brings danger to environment for the survival of mankind
Evil.Meanwhile amidine compound, as important organic synthesis intermediate, the residue processing in waste liquid and waste residue is also compeled in eyebrow
Eyelash.How to realize under temperate condition, remaining amidine compound, which is efficiently degraded into the valuable of recoverable, organises
Product are the problem of people expect to be resolved in a hurry.
The degradation technique of existing amidine analog derivative mainly uses high temperature, carries out under conditions of high pressure.Document（Chem.
Rev. 1944, 35, 351-425）In report the biodegrading process of following several amidines,（1）Non-substituted amidine is the high temperature the case where
Under（>240℃）, the corresponding nitrile of degradation generation and ammonia, the nitrile for generation of degrading with this condition are easy to happen autohemagglutination, form triazine
Product；（2）The degradation of N- substituted amidines also needs high-temperature（>240℃）, other than generating corresponding nitrile and amine, also easily generate
Toxic triazine causes new pollution.
The process is more complicated for existing amidine biodegrading process, needs higher reaction temperature, and equipment requirement is high, consumes energy, and easily produces
Raw new toxic chemical, reaction selectivity control is difficult, and product is complex, and post-processing is cumbersome, is unfavorable for product recycling profit
With and energy conservation and environmental protection.
Invention content
The object of the present invention is to provide one kind under mild reaction conditions, efficiently highly selective to resolve into amidine compound
The method of renewable nitrile and amine, catabolite is controllable, is easily isolated purification and utilization.
Amidine compound biodegrading process provided by the invention, includes the following steps：
Under nitrogen protection, under rare-earth catalysis system, by formula（Ⅰ）Shown degradation obtains formula（Ⅱ）Shown nitrile chemical combination
Object and formula（Ⅲ）Shown amine class compound；Its reaction equation is：
In above-mentioned formula, R1It is aryl or heteroaryl；
R2It is hydrogen, C1-8Alkyl, heteroaryl, aryl or aralkyl；
R3It is C1-8Alkyl, heteroaryl, aryl or aralkyl；
Wherein, the aralkyl or aryl are unsubstituted or with 1-3 substituent groups selected from the group below：C1-4Alkyl, C1-4
Alkoxy or halogen；
The rare earth catalyst is Yb (CH2SiMe3)3Or La (CH2SiMe3)3。
Formula（Ⅲ）Shown compound, is calculated with molar ratio：Formula（I）Compound/rare earth catalyst is 1/0.01-
0.10。
Formula（Ⅲ）Shown compound, reaction temperature are 0-100 DEG C.
Formula（Ⅲ）Shown compound, reaction time 0.5-36 h.
The present inventor is had found a kind of completely new rare earth catalyst method, amidine class can be spread out by long-term thoroughgoing and painstaking research
Raw degradation in a mild condition generates corresponding nitrile and amine.Compared with existing process route, the present invention has the following advantages：
1）A kind of new method of catalytic degradation amidine compound is provided, this method has reaction condition mild, easy to operate, nothing
Side reaction；
2）Catabolite is controllable, and the nitrile and amine of formation are easily recycled；
3）Wide application range of substrates.
The advantageous effect of the present invention compared with prior art：
Using the method for the present invention degradation amidine analog derivative, the nitrile quality degraded is high, high income；Degradation process is without other pairs
The generation of reaction product.Realize the degradation to amidine analog derivative under temperate condition.
Specific implementation mode
Below by embodiment, the invention will be further described, but embodiment is not intended to limit protection scope of the present invention
Embodiment 1
The degradation of N- allyl-N- phenyl benzene carbon amidines, structural formula are as follows：
Under nitrogen protection, raw material N- allyl-N- phenyl benzene carbon amidines are added（0.5 mmol）With catalyst Yb (CH2SiMe3)3(10
Mol%), toluene（1 mL）, 25 DEG C of 12 h of reaction.The yield of benzonitrile：96%；The yield of N- allyl aniline：89%.
Benzonitrile1H NMR (400 MHz, CDCl3): δ 7.64-7.58 (m, 3H), 7.48-7.44 (m,
2H).N- allyl aniline1H NMR (400 MHz, CDCl3): δ 7.17-7.14 (m, 2H), 6.70-6.68 (m,
1H), 6.61-6.60 (m, 2H), 6.00 (m, 1H), 5.15-5.14 (m, 2H), 3.75 (m, 2H)。
Embodiment 2
The degradation of N- Methyl-N-phenyl benzene carbon amidines, structural formula are as follows：
Under nitrogen protection, raw material N- Methyl-N-phenyl benzene carbon amidines are added（0.5 mmol）With catalyst Yb [N (SiMe3)2]3(10
Mol%), toluene（1 mL）, 25 DEG C of 12 h of reaction.The yield of benzonitrile：85%；The yield of methylphenylamine：81%.
Benzonitrile1H NMR (400 MHz, CDCl3): δ 7.64-7.58 (m, 3H), 7.48-7.44 (m,
2H).Methylphenylamine1H NMR (400 MHz, CDCl3): δ 7.18-7.13 (m, 2H), 6.72-6.68 (m,
1H), 6.57-6.53 (m, 2H), 3.58 (s, 1H), 2.73 (s, 3H)。
Embodiment 3
The degradation of N- Methyl-N-phenyl -2- methyl benzene carbon amidines, structural formula are as follows：
Under nitrogen protection, raw material N- Methyl-N-phenyl -2- methyl benzene carbon amidines are added（0.5 mmol）With catalyst Yb [N
(SiMe3)2]3(8 mol%), toluene（1 mL）, 25 DEG C of 7 h of reaction.The yield of o methyl benzonitrile：68%；Methylphenylamine
Yield：63%.
O methyl benzonitrile1H NMR (400 MHz, CDCl3): δ 7.58-7.56 (m, 1H), 7.50-7.46
(m, 1H), 7.32-7.24 (m, 2H), 2.53 (m, 3H).Methylphenylamine1H NMR (400 MHz, CDCl3):
δ 7.18-7.13 (m, 2H), 6.72-6.68 (m, 1H), 6.57-6.53 (m, 2H), 3.58 (s, 1H), 2.73
(s, 3H)。
Embodiment 4
The degradation of N- Methyl-N-phenyl -4- methyl benzene carbon amidines, structural formula are as follows：
Under nitrogen protection, raw material N- Methyl-N-phenyl -4- methyl benzene carbon amidines are added（0.5 mmol）With catalyst Yb [N
(SiMe3)2]3 (5mol%), toluene（1 mL）, 25 DEG C of 13 h of reaction.To the yield of methyl benzonitrile：73%；N- methyl base benzene
The yield of amine：70%.
To methyl benzonitrile1H NMR (400 MHz, CDCl3): δ 7.53-7.51 (m, 2H), 7.27-7.25
(m, 2H), 2.41 (m, 3H).Methylphenylamine1H NMR (400 MHz, CDCl3): δ 7.18-7.13 (m, 2H),
6.72-6.68 (m, 1H), 6.57-6.53 (m, 2H), 3.58 (s, 1H), 2.73 (s, 3H)。
Embodiment 5
The degradation of N- Methyl-N-phenyl -4- fundals, structural formula are as follows：
Under nitrogen protection, raw material N- Methyl-N-phenyl -4- fundals are added（0.5 mmol）With catalyst Yb [N (SiMe3)2]3
(8 mol%), toluene（1 mL）, 25 DEG C of 12 h of reaction.The yield of benzonitrile：85%；The yield of methylphenylamine：79%.
P-Cyanochlorobenzene1H NMR (400 MHz, CDCl3): δ 7.63-7.61 (m, 2H), 7.50-7.48
(m, 2H).Methylphenylamine1H NMR (400 MHz, CDCl3): δ 7.18-7.13 (m, 2H), 6.72-6.68
(m, 1H), 6.57-6.53 (m, 2H), 3.58 (s, 1H), 2.73 (s, 3H)。
Embodiment 6
The degradation of N- Methyl-N-phenyl -2- thiophene amidines, structural formula are as follows：
Under nitrogen protection, raw material N- Methyl-N-phenyl -2- thiophene amidines are added（0.5 mmol）With catalyst La [N (SiMe3)2]3
(10 mol%), toluene（1 mL）, 25 DEG C of 10 h of reaction.The yield of benzonitrile：92%；The yield of methylphenylamine：89%.
2- thiophene formonitrile HCNs1H NMR (400 MHz, CDCl3): δ 7.95-7.94 (m, 1H), 7.44-7.42
(m, 1H), 7.30-7.29 (m, 1H).Methylphenylamine1H NMR (400 MHz, CDCl3): δ 7.18-7.13
(m, 2H), 6.72-6.68 (m, 1H), 6.57-6.53 (m, 2H), 3.58 (s, 1H), 2.73 (s, 3H)。
Embodiment 7
The degradation of N, N- diethyl benzene carbon amidine, structural formula are as follows：
Under nitrogen protection, raw material N, N- diethyl benzene carbon amidine is added（0.5 mmol）With catalyst Yb [N (SiMe3)2]3(10
Mol%), N- methacrylics amine（1 mL）, 100 DEG C of 24 h of reaction.The yield of benzonitrile：79%.
Benzonitrile1H NMR (400 MHz, CDCl3): δ 7.64-7.58 (m, 3H), 7.48-7.44 (m,
2H)。
Embodiment 8
The degradation of N- phenyl benzene carbon amidines, structural formula are as follows：
Under nitrogen protection, raw material N- phenyl benzene carbon amidines are added（0.5 mmol）With catalyst Yb [N (SiMe3)2]3(10 mol%), first
Benzene（1 mL）, 100 DEG C of 36 h of reaction.The yield of benzonitrile：45%；The yield of aniline：41%.
Benzonitrile1H NMR (400 MHz, CDCl3): δ 7.64-7.58 (m, 3H), 7.48-7.44 (m,
2H).Aniline1H NMR (400 MHz, CDCl3): δ 7.24-7.03 (m, 2H), 6.81-6.56 (m, 3H),
3.54 (m, 2H)。
Finally, it should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although ginseng
It is described the invention in detail according to preferred embodiment, it will be understood by those of ordinary skill in the art that, it can be to invention
Technical solution is modified or replaced equivalently, and without departing from the spirit of the technical scheme of the invention and range, should all be covered
In scope of the presently claimed invention.
Claims (3)
1. the method that a kind of amidine compound degradation of rare earth catalyst generates nitrile and amine, which is characterized in that the specific steps are：
Under nitrogen protection, under rare-earth catalysis system, with formula（Ⅰ）Shown compound is that raw material is obtained by amidine decomposition reaction
Formula（Ⅱ）And formula（Ⅲ）Shown in nitrile and amine；Its reaction equation is：
In above-mentioned formula, R1It is aryl or heteroaryl；R2It is hydrogen, C1-8Alkyl, heteroaryl, aryl or aralkyl；R3It is C1-8Alkyl,
Heteroaryl, aryl or aralkyl；Wherein, the aralkyl or aryl are unsubstituted or take with 1-3 is selected from the group below
Dai Ji：C1-4Alkyl, C1-4Alkoxy or halogen；
The rare earth catalyst is Yb (CH2SiMe3)3Or La (CH2SiMe3)3。
2. according to the method described in claim 1, it is characterized in that, being calculated with molar ratio：Formula（Ⅰ）Compound/rare earth catalyst
For 1/0.01-0.10.
3. according to the method described in claim 1, it is characterized in that, it is 0-100 that amidine degradation, which generates nitrile and the reaction temperature of amine,
DEG C, reaction time 0.5-36 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113788743A (en) * | 2021-04-03 | 2021-12-14 | 复旦大学 | Method for catalyzing hydrogenation degradation of polypropylene ketone into ketone and alcohol with high selectivity |
| CN113788744A (en) * | 2021-04-03 | 2021-12-14 | 复旦大学 | Method for removing- [2+2+2] ring by hydrogenation of 2, 4-diacyl substituted cyclohexanol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496736A (en) * | 2014-10-23 | 2015-04-08 | 北京理工大学 | Rare earth metal compound-based cross-coupling reaction and use thereof |
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2018
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496736A (en) * | 2014-10-23 | 2015-04-08 | 北京理工大学 | Rare earth metal compound-based cross-coupling reaction and use thereof |
Non-Patent Citations (4)
| Title |
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| LAPPERT, MICHAEL F.: "Unusual metal alkyls", 《PURE AND APPLIED CHEMISTRY》 * |
| NIEMEYER, MARK: "A trigonal-bipyramidal coordinated ytterbium(III) alkyl:tris(trimethylsilylmethyl)bis(tetrahydrofuran-O)ytterbium(III)", 《 ACTA CRYSTALLOGRAPHICA, SECTION E: STRUCTURE REPORTS ONLINE》 * |
| TRIFONOV, A. A.ETAL: "Effect of ligands on the ytterbium atom on the activation of the RxYb-naphthalene sodium system in the reaction of nitrogen activation", 《ZHURNAL OBSHCHEI KHIMII》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113788743A (en) * | 2021-04-03 | 2021-12-14 | 复旦大学 | Method for catalyzing hydrogenation degradation of polypropylene ketone into ketone and alcohol with high selectivity |
| CN113788744A (en) * | 2021-04-03 | 2021-12-14 | 复旦大学 | Method for removing- [2+2+2] ring by hydrogenation of 2, 4-diacyl substituted cyclohexanol |
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