N ortho acyl substituted nitrogen-containing heterocyclic compound and process for preparing aminal iron (II) complexes thereof

Patent metadata

Field	Value
Publication number	US-9266982-B2
Application number	US-201113991044-A
Country	US
Kind code	B2
Filing date	Dec 1, 2011
Priority date	Dec 1, 2010
Publication date	Feb 23, 2016
Grant date	Feb 23, 2016

Abstract

Provided are a process for preparing an N ortho acyl substituted nitrogen-containing heterocyclic compound and an aminal iron (II) complex thereof, and the use of the complexes obtained by the process in an olefin oligomerization catalyst. The N ortho acyl substituted nitrogen-containing heterocyclic compound in the present invention is for example 2-acyl-1,10-phenanthroline or 2,6-diacetyl pyridine as shown in formula b, and the N ortho acyl substituted nitrogen-containing heterocyclic compound in the present invention is produced by a reaction of a precursor thereof in a substituted or unsubstituted nitrobenzene. Preferably the precursor shown in formula I in the present invention is produced by 1,10-phenanthroline reacting with trialkyl aluminum, or a halogenoalkyl aluminum R n AIX m , or a substituted or unsubstituted benzyl lithium Ph′CH 2 Li, followed by hydrolysis. The preparation method provided in the present invention has a few synthetic steps, an easy process, a low toxic effect, and reduces the preparation costs of the catalyst, and has a promising outlook in the industrial application.

First claim

The invention claimed is:

1. A process for preparing an N ortho acyl substituted nitrogen-containing heterocyclic compound, said process comprising oxidizing an N ortho hydrocarbyl substituted nitrogen-containing heterocyclic compound with a substituted or an unsubstituted nitrobenzene Ph′NO 2 as an oxidant to generate said N ortho acyl substituted nitrogen-containing heterocyclic compound, wherein said N ortho hydrocarbyl group is a methyl group or comprises a methylene group directly linked with the nitrogen-containing heterocyclic compound, and the five substituent groups in the benzene ring of said substituted nitrobenzene are independently selected from hydrogen, a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl or alkynyl group, a halogen, a C 1 -C 6 alkoxy group, and a nitro group,
wherein said N ortho acyl substituted nitrogen-containing heterocyclic compound is a substituted or unsubstituted 2-acyl pyridine as shown in formula B, and said process comprises oxidizing a compound as shown in formula A with the substituted or unsubstituted nitrobenzene as an oxidant to generate the compound as shown in the formula B,

wherein R 1 is selected from hydrogen, a C 1 -C 6 alkly group, a C 2 -C 6 alkenyl or alkynyl group, a phenyl group, and a substituted phenyl group, and R 2 -R 5 are independently selected from hydrogen, a C 1 -C 6 alkly group, a C 2 -C 6 alkenyl or alkynyl group, a halogen, a C 1 -C 6 alkoxy group, a nitro group, a phenyl group, and a substituted phenyl group, the five substituent groups in the benzene ring of the substituted phenyl group in R 1 -R 5 being independently selected from a C 1 -C 6 alkenyl or alkynyl group, a halogen, a C 1 -C 6 alkoxy group, and a nitro group.

2. The process according to claim 1 , wherein the N ortho acyl substituted nitrogen-containing heterocyclic compound is 2,6-diacetyl pyridine,and said process comprises oxidizing 2,6-diethyl pyridine as shown in formula I′ with the substituted or unsubstituted nitrobenzene as an oxidant to generate 2,6-diacetyl pyridine as shown in formula b′:

3. A process for preparing an N ortho acyl substituted nitrogen-containing heterocyclic compound, said process comprising oxidizing an N ortho hydrocarbyl substituted nitrogen-containing heterocyclic compound with a substituted or an unsubstituted nitrobenzene Ph′NO 2 as an oxidant to generate said N ortho acyl substituted nitrogen-containing heterocyclic compound, wherein said N ortho hydrocarbyl group is a methyl group or comprises a methylene group directly linked with the nitrogen-containing heterocyclic compound, and the five substituent groups in the benzene ring of said substituted nitrobenzene are independently selected from hydrogen, a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl or alkynyl group, a halogen, a C 1 -C 6 alkoxy group, and a nitro group, wherein the N ortho acyl substituted nitrogen-containing heterocyclic compound is a compound as shown in formula B″, and said process comprises oxidizing a compound as shown in formula A″ with the substituted or unsubstituted nitrobenzene as an oxidant to generate the compound as shown in formula B″,

wherein R 1 is selected from hydrogen, a C 1 -C 6 alkyl group, a C 2 -C 6 an alkenyl or alkynyl group, a phenyl group, and a substituted phenyl group, and R 2 -R 3 and R 6 -R 10 are independently selected from hydrogen, a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl or alkynyl group, a halogen, a C 1 -C 6 alkoxy group, a nitro group, a phenyl group, and a substituted phenyl group, the five substituent groups in the benzene ring of the substituted phenyl group in R 1 -R 10 being independently selected from a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl or alkynyl group, a halogen, a C 1 -C 6 alkoxy group, and a nitro group.

4. The process according to claim 3 , wherein the N ortho acyl substituted nitrogen-containing heterocyclic compound is 2-acyl-1,10-phenanthroline, and said process comprises oxidizing a compound as shown in formula I with the substituted or unsubstituted nitrobenzene as an oxidant to generate 2-acyl-1,10-phenanthroline as shown in formula b,

wherein R is a C 1 -C 6 alkyl group, a benzyl group, or a substituted benzyl group, R′ is hydrogen or an alkyl group less than R by a CH 2 , or a substituted phenyl group or an unsubstituted phenyl group, and when R is a substituted benzyl group, the five substituent groups in the benzene ring thereof are independently selected from a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl or alkynyl group, a halogen, a C 1 -C 6 alkoxy group, and a nitro group.

5. The process according to claim 4 , wherein the oxidation reaction is carried out at a temperature ranging from 200 to 220° C. under reflux, and the oxidation reaction time ranges from 10 to 100h.

6. The process according to claim 4 , wherein the molar ratio of the compound as shown in formula I to the substituted or unsubstituted nitrobenzene ranges from 1:0.5 to 1:30.

7. The process according to claim 4 , wherein said compound as shown in formula I is prepared by the following steps: reacting 1,10-phenanthroline as shown in formula a with a trialkyl aluminum, or a halogenated alkylaluminum R n AIX m , or a substituted or unsubstituted benzyl lithium Ph′CH 2 Li, followed by hydrolysis to obtain the compound as shown in formula I,

and in the halogenated alkylaluminum R n AIX m , R can be the same or different C 1 -C 6 alkyl groups, X is a halogen, 1≦n≦3, 0≦m≦2, and m+n=3.

8. The process according to claim 7 , wherein the hydrolysis is carried out in water or alcohol.

9. The process according to claim 7 , wherein the molar ratio of said 1,10-phenanthroline to R n AIX m , or Ph′CH 2 Li ranges from 1:0.5 to 1:4.5, the reaction temperature of said 1,10-phenanthroline with R n AIX m , or Ph′CH 2 Li ranges from −60 to −80° C., and the hydrolysis temperature ranges from −60 to −0° C.

10. The process according to claim 7 , wherein the reaction temperature of said 1,10-phenanthroline with R n AIX m , or Ph′CH 2 Li ranges from −60 to −70° C., which after a period of reaction is raised to 20 to 40° C., at which the reaction is continued.

11. The process according to claim 1 , wherein R 1 is selected from hydrogen, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, and the substituted phenyl group, and wherein R 2 -R 5 are independently selected from hydrogen, a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, fluorine, chlorine, bromine, a methoxy group, an ethoxy group, a propoxy group, a nitro group, a phenyl group, and the substituted phenyl group.

12. The process according to claim 3 , wherein R 1 is selected from hydrogen, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, and the substituted phenyl group, and wherein R 2 -R 3 and R 6 -R 10 are independently selected from hydrogen, a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, fluorine, chlorine, bromine, a methoxy group, an e

Assignees

• Liu Jun
• Zheng Mingfang
• Li Weizhen
• Zhang Haiying
• Wang Huaijie
• Zhou Yu
• Li Tonglin
• Zhao Lan
• Wu Hongfei
• Xie Mingjun
• Wu Chunhong
• Jia Zhiguang
• Qi Yanping
• Wang Jilong
• China Petroleum & Chemical
• Beijing Res Inst Chem Ind

Inventors

• Liu Jun
• Zheng Mingfang
• Li Weizhen
• Zhang Haiying
• Wang Huaijie
• Zhou Yu
• Li Tonglin
• Zhao Lan
• Wu Hongfei
• Xie Mingjun
• Wu Chunhong
• Jia Zhiguang
• Qi Yanping
• Wang Jilong

Classifications

• B01J2531/842

  Iron · CPC title

• C08F110/02 Primary

  Ethene · CPC title

• C07D471/04

  Ortho-condensed systems · CPC title

• B01J2531/0241

  Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution · CPC title

• B01J31/183 Primary

  with more than one complexing nitrogen atom, e.g. phenanthroline · CPC title