Chain multiyne compound, preparation method and application thereof

Patent metadata

Field	Value
Publication number	US-10287225-B2
Application number	US-201715811277-A
Country	US
Kind code	B2
Filing date	Nov 13, 2017
Priority date	May 13, 2015
Publication date	May 14, 2019
Grant date	May 14, 2019

Abstract

The present invention relates to fields of organic chemistry and organometallic chemistry. The present invention discloses a chain multiyne compound, a preparation method thereof and an application in synthesizing a fused-ring metallacyclic compound. A structure of the chain multiyne compound in the present invention is shown as Formula I below. The present invention also provides a preparation method of the chain multiyne compound and an application thereof in a synthesis of a fused-ring metallacyclic compound. The chain multiyne compound disclosed in the present invention has multiple functional groups and the structure of the chain multiyne compound is adjustable. The chain multiyne compound can also be used to synthesize the fused-ring metallacyclic compound efficiently. The preparation method of the chain multiyne compound disclosed in the present invention is simple, which can be used to prepare the chain multiyne compound rapidly and efficiently.

First claim

What is claimed is:

1. A chain multiyne compound of Formula I:

wherein, X is any one of —O—, —S—, —CH 2 —, —C(CH 3 ) 2 —, —CHCH 3 —, —C(COOMe) 2 -, —C(COOEt) 2 -, —C(COCH 3 )(COOMe)-, —C(Cy)(COOMe)-, —C(CH 2 CH 2 Br) 2 —, —C(CN) 2 —, —C(NO 2 ) 2 —, —SiH 2 —, —SiMe 2 -, —SiPh 2 -, —NH—,

R 1 is any one of nitrile group, acetenyl,

R 2 and R 3 are independently any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, methoxyl, ethoxyl, n-propoxyl, isopropoxyl, methylthio group, ethylthio group, cyclopropyl, cyclohexyl,

benzyl and phenethyl;
wherein m and n are independently integers from 1-6, and m+n<8.

2. A chain multiyne compound of Formula I:

wherein X is any one of —O—, —S—, —CR 4 R 5 —, —SiR 6 R 7 — and —NR 8 —, R 4 , R 5 , R 6 , R 7 and R 8 are independently any one of hydrogen, C 1 -C 20 alkyl, C 1 -C 20 ester group, C 1 -C 20 acyl, C 3 -C 20 cycloalkyl, C 1 -C 20 alkyl halide, nitrile group, nitryl, substituted or unsubstituted aryl and

R 9 is any one of C 1 -C 8 alkyl and substituted or unsubstituted phenyl;
R 1 is any one of nitrile group, substituted or unsubstituted C 2 -C 30 alkynyl, substituted or unsubstituted C 4 -C 30 multiyne, substituted or unsubstituted C 3 -C 30 cumulene group, without containing a structure unit of —C≡CCH(OH)C≡C—;
R 2 and R 3 are independently any one of hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted C 1 -C 8 alkyl, substituted or unsubstituted C 1 -C 8 alkoxy, substituted or unsubstituted C 1 -C 8 alkylthiol, substituted or unsubstituted C 3 -C 8 cycloalkyl and substituted or unsubstituted C 2 -C 8 alkynyl, without containing a structure unit of —C≡CCH(OH)C≡C—; and
m and n are independently integers from 1-6, and m+n<8;
wherein the multiyne compound is any one of the following compounds:

3. A method of synthesizing a fused-ring metallacyclic compound, comprising reacting the chain multiyne compound of Formula I with a metal complex

wherein X is any one of —O—, —S—, —CR 4 R 5 —, —SiR 6 R 7 — and —NR 8 —; R 4 , R 5 , R 6 , R 7 and R 8 are independently any one of hydrogen, C 1 -C 20 alkyl, C 1 -C 20 ester group, C 1 -C 20 acyl, C 3 -C 20 cycloalkyl, C 1 -C 20 alkyl halide, nitrile group, nitryl, substituted or unsubstituted aryl and

R 9 is any one of C 1 -C 8 alkyl and substituted or unsubstituted phenyl;
R 1 is any one of nitrile group, substituted or unsubstituted C 2 -C 30 alkynyl, substituted or unsubstituted C 4 -C 3 o multiyne, substituted or unsubstituted C 3 -C 30 cumulene group, without containing a structure unit of —C≡CCH(OH)C≡C—;
R 2 and R 3 are independently any one of hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted C 1 -C 8 alkyl, substituted or unsubstituted C 1 -C 8 alkoxy, substituted or unsubstituted C 1 -C 8 alkylthiol, substituted or unsubstituted C 3 -C 8 cycloalkyl and substituted or unsubstituted C 2 -C 8 alkynyl, without containing a structure unit of —C≡CCH(OH)C≡C—; and
m and n are independently integers from 1-6, and m+n<8;
wherein the metal complex is DE a L b ;
D is any one of Fe, Co, Ni, Ru, Mn, Re, Cr, Mo, W, V, Nb, Ta, Ti, Zr, Hf, Rh, Pd, Ir, Pt and Os;
E is any one of H, halogen, SCN and CN;
L is any one of a phosphine ligand, a CO ligand, a pyridine ligand, a N-heterocyclic carbene ligand, a nitrile ligand and an isocyanoid ligand; and
a and b are independently integers from 0-6.

4. The method according to claim 3 , wherein
L is any one of trimethylphosphine, triethylphosphine, tripropylphosphine, tri-isopropylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, methylpyridine, ethylpyridine, 1,4-bipyridine, 1,2-bis(4-pyridyl) ethylene, vinylpyridine, pyridineboronic acid, aminopyridine, cyanopyridine, pyridinethiol, ethynylpyridine, dimethylaminopyridine, ethylene pyridine, phenylpyridine, 1,2-bis(4-pyridyl)ethane, imidazole N-heterocyclic carbene, imidazoline N-heterocyclic carbene, thiazole N-heterocyclic carbene, triazole N-heterocyclic carbene, acetonitrile, propionitrile, benzonitrile, cyclohexylisocyanide, tert-butylisocyanide and phenylisocyanide;
a and b are independently integers from 0-6; when a≥2, E is different or is the same and when b≥2, L is different or is the same.

5. The method according to claim 3 , the metal complex is any one of OsCl 2 (PPh 3 ) 3 , RuCl 2 (PPh 3 ) 3 , RhCl(PPh 3 ) 3 and IrHCl 2 (PPh 3 ) 3 .

Assignees

• Univ Xiamen

Inventors

• Xia Haiping
• Zhuo Qingde
• Lin Jianfeng
• Zhou Xiaoxi
• Chen Zhixin
• Shao Yifan
• Zhang Hong
• He Xumin

Classifications

• C07D333/24

  Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals · CPC title

• C07C69/606

  having only {or additionally} carbon-to-carbon triple bonds as unsaturation in the carboxylic acid moiety · CPC title

• C07C2601/08

  the ring being saturated · CPC title

• C07F15/0033

  Iridium compounds · CPC title

• C07C43/1787

  containing six-membered aromatic rings and having unsaturation outside the aromatic rings · CPC title