CN113735730B - Preparation method of acyl primary amine - Google Patents
Preparation method of acyl primary amine Download PDFInfo
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- CN113735730B CN113735730B CN202111029287.7A CN202111029287A CN113735730B CN 113735730 B CN113735730 B CN 113735730B CN 202111029287 A CN202111029287 A CN 202111029287A CN 113735730 B CN113735730 B CN 113735730B
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- acyl
- catalyst
- primary amine
- ammonium chloride
- terminal olefin
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- -1 acyl primary amine Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 150000001336 alkenes Chemical group 0.000 claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical group [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000001273 butane Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 abstract description 14
- 230000007547 defect Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 150000001408 amides Chemical class 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- DOZZSWAOPDYVLH-ZETCQYMHSA-N (2s)-2-phenylpropanamide Chemical compound NC(=O)[C@@H](C)C1=CC=CC=C1 DOZZSWAOPDYVLH-ZETCQYMHSA-N 0.000 description 2
- VYIBCOSBNVFEIW-UHFFFAOYSA-N 3-phenylpropanamide Chemical compound NC(=O)CCC1=CC=CC=C1 VYIBCOSBNVFEIW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- UVBXZOISXNZBLY-UHFFFAOYSA-L palladium(2+);triphenylphosphane;diacetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UVBXZOISXNZBLY-UHFFFAOYSA-L 0.000 description 2
- MXQOYLRVSVOCQT-UHFFFAOYSA-N palladium;tritert-butylphosphane Chemical compound [Pd].CC(C)(C)P(C(C)(C)C)C(C)(C)C.CC(C)(C)P(C(C)(C)C)C(C)(C)C MXQOYLRVSVOCQT-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- CGGSBFOEANJHGY-UHFFFAOYSA-N 4-bis(2,3,4,5,6-pentafluorophenyl)phosphanylbutyl-bis(2,3,4,5,6-pentafluorophenyl)phosphane Chemical group FC1=C(F)C(F)=C(F)C(F)=C1P(C=1C(=C(F)C(F)=C(F)C=1F)F)CCCCP(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F CGGSBFOEANJHGY-UHFFFAOYSA-N 0.000 description 1
- 238000010693 amine synthesis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 150000003140 primary amides Chemical class 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003334 secondary amides Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003511 tertiary amides Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of acyl primary amine. The preparation method of the acyl primary amine comprises the following steps: heating terminal olefin, carbon monoxide and ammonium chloride in the presence of a catalyst to react to obtain acyl primary amine; wherein the catalyst is Pd% t Bu 3 P) 2 、Pd(Ph 3 P) 2 、Pd(dppp) 2 、Pd(d F ppb) 2 At least one of the terminal olefins having the formula R-ch=ch 2 R is any group. Under the action of a specific catalyst, linear or branched acyl primary amine can be synthesized with high regioselectivity, and the defect of the prior art in the aspect of regioselectivity of the acyl amine compound synthesis reaction is overcome.
Description
Technical Field
The invention belongs to the field of organic compound synthesis, and relates to a preparation method of acyl primary amine.
Background
The acylamine compound is a fine chemical widely used in industrial production, and the research of the synthesis method thereof has important significance. One of the methods for directly synthesizing the acylamine compound is to react olefin, carbon monoxide and nitrogen-containing compound under the catalysis of transition metal and ligand thereof, and finally obtain the acylamine product. The raw materials of the nitrogen-containing compound in the synthesis method can be primary amine, secondary amine and ammonium chloride, and the products of the raw materials are secondary amide, tertiary amide and primary amide correspondingly; the transition metal to be reacted may be Ni, pt, cu, pd or the like. Since the first report of this kind of synthesis method by foreign chemists Reppe, many chemists at home and abroad make a great contribution to the improvement of this synthesis method. However, the transition metal catalytic synthesis of the compound has a defect in the aspect of regioselectivity, and a new catalytic synthesis method is urgently needed to be developed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of acyl primary amine, so as to improve the regioselectivity of the acyl primary amine synthesis reaction.
In order to achieve the above object, the present invention provides a method for producing an acyl primary amine, comprising the steps of: heating terminal olefin, carbon monoxide and ammonium chloride in the presence of a catalyst to react to obtain acyl primary amine; the catalyst is Pd% t Bu 3 P) 2 、Pd(Ph 3 P) 2 、Pd(dppp) 2 、Pd(d F ppb) 2 At least one of the terminal olefins having the formula R-ch=ch 2 Wherein R is any group.
Herein, pd @ is t Bu 3 P) 2 Refers to bis (tri-tert-butylphosphine) palladium with CAS number 53199-31-8; pd (Ph) 3 P) 2 Ph in (3) 3 P is triphenylphosphine, pd (Ph 3 P) 2 At least one of bis (triphenylphosphine) palladium dichloride (CAS number 13965-03-2), bis (triphenylphosphine) palladium (II) acetate (CAS number 14588-08-0), etc.; pd (dppp) 2 Wherein dppp is 1, 3-bis (diphenylphosphino) propane, pd (dppp) 2 Can be selected from [1, 3-bis-diphenylphosphinopropane ]]At least one of palladium chloride (CAS number 59831-02-6), etc.; pd (d) F ppb) 2 D in (d) F ppb is 1, 4-bis (di (pentafluorophenyl) -phosphino) butane, pd (d) F ppb) 2 D in (d) F ppb refers to 1, 4-bis (pentafluorophenyl) -phosphino) butane.
The preparation method can synthesize linear (namely) Or branch (i.e.)>) Amides, productsRate of>50％。
Preferably, the primary acyl amine isThe catalyst is Pd (dppp) 2 、Pd(d F ppb) 2 At least one of them. When the catalyst is Pd (dppp) 2 、Pd(d F ppb) 2 At least one of the above is a linear amide, and a branched amide is not synthesized.
Preferably, the catalyst is Pd (d F ppb) 2 . Compared with Pd (dppp) 2 In Pd (d) F ppb) 2 As a catalyst, the yield of the obtained linear amide is higher.
Preferably, the primary acyl amine isThe catalyst is Pd% t Bu 3 P) 2 、Pd(Ph 3 P) 2 At least one of them. When the catalyst is Pd% t Bu 3 P) 2 、Pd(Ph 3 P) 2 At least one of the above is branched, and the linear amide is not synthesized.
Preferably, R is phenyl.
Preferably, the heating reaction is carried out under closed conditions.
Preferably, the molar ratio of terminal olefin, ammonium chloride and catalyst is: ammonium chloride: catalyst=1:1-3:0.03-1, the gas pressure of the carbon monoxide is 20-40atm, the temperature of the heating reaction is 100-140 ℃, and the time of the heating reaction is 20-28 h. Under the synthesis reaction conditions, the yield of the branched or linear amide obtained is > 50%.
Further preferably, the molar ratio of terminal olefin, ammonium chloride and catalyst is: ammonium chloride: catalyst=1:2:0.05, the gas pressure of the carbon monoxide was 30atm, the temperature of the heating reaction was 120 ℃, and the time of the heating reaction was 24 hours, so that the yield of the branched or linear amide obtained was > 80%.
Preferably, the heating reaction is performed in a stirred state.
Preferably, the heating reaction is carried out in the presence of NMP (N-methylpyrrolidone).
Preferably, the molar ratio of NMP to terminal olefin is 3-7:1. Further preferably, the molar ratio of NMP to terminal olefin is 5:1.
Compared with the prior art, the invention has the beneficial effects that: the invention makes the terminal olefin, carbon monoxide and ammonium chloride in Pd% t Bu 3 P) 2 、Pd(Ph 3 P) 2 、Pd(dppp) 2 、Pd(d F ppb) 2 The linear or branched primary acylamine can be synthesized with high regioselectivity by heating reaction under the catalysis of at least one of the components, and the defect of the prior art in the aspect of regioselectivity of the synthesis reaction of the acylamine compound is overcome.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples. It will be appreciated by persons skilled in the art that the specific embodiments described herein are for purposes of illustration only and are not intended to be limiting.
In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, are commercially available.
Example 1
Example 1 provides a process for the preparation of an acyl primary amine comprising the steps of: in a glove box, 2.0 mmol of NH 4 Cl, 0.05 mmol Pd% t Bu 3 P) 2 And 5.0 ml of NMP was added to a dry glass flask, stirred at room temperature for 10 minutes, 114. Mu.l (1.0 mmol) of styrene was added, the glass flask was placed in an autoclave, then the glove box was removed, the air in the autoclave was evacuated, CO gas (30 atm) was filled, the reaction mixture was stirred at 120℃for 24 hours, after the completion of the reaction, the autoclave was cooled to room temperature, and the air pressure was reduced to atmospheric pressure in a fume hood, to obtain a primary acylamine. The product is led throughThe product was detected by GC and GC-MS and was (S) -2-phenylpropionamide in 81% yield using n-hexane as internal standard.
Example 2
Example 2 provides a process for the preparation of primary acyl amines using in addition to 0.05 mmole Pd (Ph 3 P) 2 Replaced Pd% t Bu 3 P) 2 Except for this, the procedure was the same as in example 1. The product was detected by GC and GC-MS and was measured to be (S) -2-phenylpropionamide in 84% yield using n-hexane as internal standard.
Example 3
Example 3 provides a process for the preparation of primary acyl amines except that 0.05 millimoles Pd (dppp) 2 Replaced Pd% t Bu 3 P) 2 Except for this, the procedure was the same as in example 1. The product was detected by GC and GC-MS and was measured as 3-phenylpropionamide with 82% yield using n-hexane as internal standard. 1 H NMR(400MHz,CDCl 3 )δ2.51(t,J＝7.6Hz,2H),2.95(t,J＝8.0Hz,2H),5.59(br,1H),6.03(br,1H),7.19-7.21(m,3H),7.26-7.30(m,2H)； 13 C NMR(100MHz,CDCl 3 )δ31.4,37.5,126.3,128.3,128.6,140.7,174.9。HRMS(ESI)calcd.for C9H11NONa[M+Na]:172.0733,found:172.0734。
Example 4
Example 4 provides a process for the preparation of primary acyl amines, except for 0.05 mmol Pd (d F ppb) 2 Replaced Pd% t Bu 3 P) 2 Except for this, the procedure was the same as in example 1. The product was detected by GC and GC-MS and was 3-phenylpropionamide in 93% yield using n-hexane as internal standard.
The inventors found during the course of the study that the catalyst was prepared as Pd (d F ppb) 2 As a catalyst, compared with Pd% t Bu 3 P) 2 、Pd(Ph 3 P) 2 、Pd(dppp) 2 The yield of the obtained acyl primary amine is obviously higher as the catalyst.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (5)
1. A process for the preparation of an acyl primary amine, comprising the steps of: heating terminal olefin, carbon monoxide and ammonium chloride in the presence of a catalyst to react to obtain acyl primary amine; the catalyst is Pd (d) F ppb) 2 The structural formula of the terminal olefin is R-CH=CH 2 The method comprises the steps of carrying out a first treatment on the surface of the The acyl primary amine isThe method comprises the steps of carrying out a first treatment on the surface of the Wherein R is phenyl, pd (d F ppb) 2 D in (d) F ppb is 1, 4-bis (pentafluorophenyl) -phosphino) butane.
2. The process according to claim 1, wherein the heating reaction is carried out under closed conditions.
3. The method of claim 2, wherein the molar ratio of terminal olefin, ammonium chloride and catalyst is terminal olefin: ammonium chloride: catalyst=1:1-3:0.03-1, the gas pressure of the carbon monoxide is 20-40atm, the temperature of the heating reaction is 100-140 ℃, and the time of the heating reaction is 20-28 h.
4. A process according to claim 3, wherein the molar ratio of terminal olefin, ammonium chloride and catalyst is terminal olefin: ammonium chloride: catalyst=1:2:0.05, the gas pressure of the carbon monoxide is 30atm, the temperature of the heating reaction is 120 ℃, and the time of the heating reaction is 24h.
5. The production method according to claim 2, wherein the heating reaction is performed in a stirred state.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107935878A (en) * | 2017-11-20 | 2018-04-20 | 华东师范大学 | A kind of method that primary amide is prepared by alkene, carbon monoxide and ammonia |
| CN108569977A (en) * | 2017-03-08 | 2018-09-25 | 中国科学技术大学 | A kind of preparation method of primary fatty amides |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108569977A (en) * | 2017-03-08 | 2018-09-25 | 中国科学技术大学 | A kind of preparation method of primary fatty amides |
| CN107935878A (en) * | 2017-11-20 | 2018-04-20 | 华东师范大学 | A kind of method that primary amide is prepared by alkene, carbon monoxide and ammonia |
Non-Patent Citations (3)
| Title |
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| 1-（2,6-二氯苯基）-2-吲哚酮及相关物质的HPLC分离分析;吉琼梅 等;《色谱》;第18卷(第1期);第55-56页 * |
| Bao Gao et al..Palladium-catalyzed regiodivergent hydroaminocarbonylation of alkenes to primary amides with ammonium chloride.《Chem. Sci.》.2017,第9卷第380-386页. * |
| Palladium-catalyzed regiodivergent hydroaminocarbonylation of alkenes to primary amides with ammonium chloride;Bao Gao et al.;《Chem. Sci.》;第9卷;第380-386页 * |
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