US 12,331,007 B2
Use of a multidentate phosphite ligand in the catalytic synthesis of adiponitrile
Zhirong Chen, Zhejiang (CN); Wenbin Wu, Zhejiang (CN); Hong Yin, Zhejiang (CN); Zengshi Zha, Zhejiang (CN); Keyan Wang, Zhejiang (CN); Li Ma, Zhejiang (CN); Guodong Huang, Zhejiang (CN); Guiyang Zhou, Zhejiang (CN); and Yong Xu, Zhejiang (CN)
Assigned to ZHEJIANG NHU CO., LTD., Zhejiang (CN); ZHEJIANG NHU SPECIAL MATERIALS CO., LTD., Zhejiang (CN); and ZHEJIANG NHU NYLON MATERIALS CO., LTD., Zhejiang (CN)
Appl. No. 17/800,452
Filed by ZHEJIANG NHU CO., LTD., Zhejiang (CN); ZHEJIANG NHU SPECIAL MATERIALS CO., LTD., Zhejiang (CN); and ZHEJIANG NHU NYLON MATERIALS CO., LTD., Zhejiang (CN)
PCT Filed Jun. 21, 2022, PCT No. PCT/CN2022/100184
§ 371(c)(1), (2) Date Aug. 17, 2022,
PCT Pub. No. WO2023/060929, PCT Pub. Date Apr. 20, 2023.
Claims priority of application No. 202111203682.2 (CN), filed on Oct. 15, 2021.
Prior Publication US 2024/0336560 A1, Oct. 10, 2024
Int. Cl. C07C 253/10 (2006.01); B01J 31/18 (2006.01); B01J 37/04 (2006.01); C07F 9/06 (2006.01); C07F 9/6571 (2006.01)
CPC C07C 253/10 (2013.01) [B01J 31/185 (2013.01); B01J 37/04 (2013.01); C07F 9/062 (2013.01); C07F 9/6571 (2013.01); B01J 2231/322 (2013.01); B01J 2231/52 (2013.01); B01J 2531/004 (2013.01); B01J 2531/847 (2013.01)] 12 Claims
 
1. A method of catalytic synthesis of adiponitrile using a multidentate phosphite ligand, wherein the multidentate phosphite ligand is a compound represented by a following general formula (I), the method comprising:
subjecting butadiene and hydrocyanic acid to a primary hydrocyanation reaction in the presence of a first catalyst;
subjecting a branched mononitrile mixture to an isomerization reaction of branched mononitriles in a presence of a second catalyst, wherein the branched mononitrile mixture is separated from a product obtained in the primary hydrocyanation reaction; and
subjecting a linear mononitrile mixture and hydrocyanic acid to a secondary hydrocyanation reaction in the presence of a third catalyst and a promoter to obtain a product containing adiponitrile, wherein the linear mononitrile mixture is separated from the products obtained in the primary hydrocyanation reaction and the isomerization reaction;
wherein the first catalyst, the second catalyst, and the third catalyst are identical or different, and each of the catalysts comprises a phosphite ligand-zero-valent nickel complex formed of a nickel precursor and the multidentate phosphite ligand:

OG Complex Work Unit Chemistry
in formula (1), R0 is —O-A4, H, an C1˜6 alkyl group, a substituted or unsubstituted C3˜10 cycloalkyl group, or a substituted or unsubstituted C6˜20 aryl group;
R11 to R16 are identical to or different from each other, and each independently represents hydrogen, an C1˜6 alkyl group, a substituted or unsubstituted C3˜10 cycloalkyl group, or a substituted or unsubstituted C6˜20 aryl group;
A1, A2, A3, and A4 are identical to or different from each other, and each independently is

OG Complex Work Unit Chemistry
each of R21 and each of R22 are identical to or different from each other, and each of R21 and each of R22 is independently H, a substituted or unsubstituted C1˜6 alkyl group, a substituted or unsubstituted C3˜10 cycloalkyl group, a C1˜6 acyl group, or a substituted or unsubstituted C6˜20 aryl group; and
R21 and R22 may bond to form a ring via a single bond, an C1˜6 alkylene group, a phenylene group, or a C1˜6 alkyl substituted phenylene group;
Q is a single bond, an C1˜3 alkylene group, an oxygen atom, a nitrogen atom, or an C1˜3 alkylene group containing an oxygen atom or a nitrogen atom.