Continuous carbonylation processes

Patent metadata

Field	Value
Publication number	US-10221150-B2
Application number	US-201615550217-A
Country	US
Kind code	B2
Filing date	Feb 12, 2016
Priority date	Feb 13, 2015
Publication date	Mar 5, 2019
Grant date	Mar 5, 2019

Abstract

Provided are processes for monitoring and maintaining continuous carbonylation of epoxides or lactones. Processes include measuring parameters affecting the rate of the carbonylation reaction and adding supplemental replacement catalyst replacement components to maintain a constant rate of carbonylation.

First claim

What is claimed is:

1. A process for continuous carbonylation of an epoxide or lactone feedstock, comprising:
continuously reacting an epoxide or lactone feedstock with carbon monoxide in the presence of a carbonylation catalyst in a carbonylation reaction vessel,
wherein the carbonylation catalyst comprises a Lewis acid and a metal carbonyl, and
wherein at a start time of the process, the carbonylation reaction vessel contains an initial concentration of the Lewis acid and an initial concentration of the metal carbonyl; and

adding to the carbonylation reaction vessel, at a time after the start time of the process, a catalyst replacement component which is different from the carbonylation catalyst,
wherein the catalyst replacement component comprises the Lewis acid, a precursor to the Lewis acid, the metal carbonyl, and a precursor to the metal carbonyl,
wherein the precursor to the metal carbonyl is a neutral metal carbonyl complex, and
wherein the precursor to the Lewis acid is:

wherein:
each R q is independently C 1-12 aliphatic or aryl,
wherein the aryl is unsubstituted or substituted with one or more substituents selected from the group consisting of halogen; —(CH 2 ) 0-4 R ∘ ; —(CH 2 ) 0-4 OR ∘ ; —O—(CH 2 ) 0-4 C(O)OR ∘ ; —(CH 2 ) 0-4 CH(OR ∘ ) 2 ; —(CH 2 ) 0-4 SR ∘ ; —(CH 2 ) 0-4 Ph; —(CH 2 ) 0-4 O(CH 2 ) 0-1 Ph; —CH═CHPh; —NO 2 ; —CN; —N 3 ; —(CH 2 ) 0-4 N(R ∘ ) 2 ; —(CH 2 ) 0-4 N(R ∘ C(O)R ∘ ; —N(R ∘ C(S)R ∘ ; —(CH 2 ) 0-4 N(R ∘ )C(O)NR ∘ 2 ; —N(R ∘ )C(S)NR ∘ 2 ; —(CH 2 ) 0-4 N(R ∘ )C(O)OR ∘ ; —N(R ∘ )N(R ∘ )C(O)R ∘ ; —N(R ∘ )N(R ∘ )C(O)NR ∘ 2 ; —N(R ∘ )N(R ∘ )C(O)OR ∘ ; —(CH 2 ) 0-4 C(O)R ∘ ; —C(S)R ∘ ; —(CH 2 ) 0-4 C(O)OR ∘ ; —(CH 2 ) 0-4 C(O)N(R ∘ ) 2 ; —(CH 2 ) 0-4 C(O)SR ∘ ; —(CH 2 ) 0-4 C(O)OSiR ∘ 3 ; —(CH 2 ) 0-4 OC(O)R ∘ ; —OC(O)(CH 2 ) 0-4 SR ∘ ; —SC(S)SR ∘ ; —(CH 2 ) 0-4 SC(O)R ∘ ; —(CH 2 ) 0-4 C(O)NR ∘ 2 ; —C(S)NR ∘ 2 ; —C(S)SR ∘ , —SC(S)SR ∘ ; —(CH 2 ) 0-4 OC(O)NR ∘ 2 ; —C(O)N(OR ∘ )R ∘ , —C(O)C(O)R ∘ , —C(O)CH 2 C(O)R ∘ ; —C(NOR ∘ )R ∘ ; —(CH 2 ) 0-4 SSR ∘ ; —(CH 2 ) 0-4 S(O) 2 R ∘ ; —(CH 2 ) 0-4 S(O) 2 OR ∘ ; —(CH 2 ) 0-4 OS(O) 2 R ∘ ; —S(O) 2 NR ∘ 2 ; —(CH 2 ) 0-4 S(O)R ∘ ; —N(R ∘ )S(O) 2 NR ∘ 2 ; —N(R ∘ )S(O) 2 R ∘ ; —N(OR ∘ )R ∘ ; —C(NH)NR ∘ 2 ; —P(O) 2 R ∘ ; —P(O)R ∘ 2 ; —OP(O)R ∘ 2 ; —OP(O)(OR ∘ ) 2 ; SiR ∘ 3 ; —(C 1-4 straight or branched alkylene)O—N(R ∘ ) 2 ; and —(C 1-4 straight or branched alkylene)C(O)O—N(R ∘ ) 2 ,
wherein R ∘ at each occurrence is
independently hydrogen, C 1-8 aliphatic, —CH 2 Ph, or —O(CH 2 ) 0-1 Ph; or
a 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; or
wherein two independent occurrences of R ∘ , taken together with their intervening atom(s), form a 3-12-membered saturated, partially unsaturated, or aryl mono- or polycyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur;

M is a metal atom;
R d at each occurrence is
independently hydrogen, halogen, —OR 4 , —NR y 2 , —SR y , —CN, —NO 2 , —SO 2 R y , —SOR y , —SO 2 NR y 2 ; —CNO, —NR y SO 2 R y , —NCO, —N 3 , or —SiR y 3 ; or an optionally substituted group selected from the group consisting of:
C 1-20 aliphatic;
C 1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
6- to 10-membered aryl;
5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; and
4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; or

wherein two or more R d groups may be taken together to form one or more optionally substituted rings;
each R y is
independently hydrogen; or an optionally substituted group selected the group consisting of:
acyl;
carbamoyl,
arylalkyl;
6- to 10-membered aryl;
C 1-12 aliphatic;
C 1-12 heteroaliphatic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
an oxygen protecting group; and
a nitrogen protecting group; or

wherein two R y on the same nitrogen atom are taken with the nitrogen atom to form an optionally substituted 4- to 7-membered heterocyclic ring having 0-2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and
each R 4 is independently a hydroxyl protecting group or R y ;

R 1a , R 1a′ , R 2a , R 2a′ , R 3a , and R 3a′ are
independently hydrogen, halogen, —OR 4 , —NR y 2 , —SR y , —CN, —NO 2 , —SO 2 R y , —SOR y , —SO 2 NR y 2 ; —CNO, —NR y SO 2 R y , —NCO, —N 3 , or —SiR y 3 ; or an optionally substituted group selected from the group consisting of:
C 1-20 aliphatic;
C 1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
6- to 10-membered aryl;
5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; and
4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; or

wherein any of (R 2a′ and R 3′ ), (R 2a and R 3a ), (R 1a and R 2a ), and (R 1a′ and R 2′ ) may optionally be taken together with the carbon atoms to which they are attached to form one or more rings which may in turn be substituted with one or more R y groups; and

R 4a is selected from the group consisting of:

wherein:
R c at each occurrence is
independently hydrogen, halogen, —OR 4 , —NR y 2 , —SR y , —CN, —NO 2 , —SO 2 R y , —SOR y , —SO 2 NR y 2 ; —CNO, —NR y SO 2 R y , —NCO, —N 3 , or —SiR y 3 ; or an optionally substituted group selected from the group consisting of:
 C 1-20 aliphatic;
 C 1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
 6- to 10-membered aryl;
 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; and
 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; or
wherein two or more R c groups may be taken together with the carbon atoms to which they are attached and any intervening atoms to form one or more rings; or
wherein two R c groups are attached to the same carbon atom, they may be taken together along with the carbon atom to which they are attached to form a moiety selected from the group consisting of: a 3- to 8-membered spirocyclic ring, a carbonyl, an oxime, a hydrazone, an imine; and an optionally substituted alkene;

Y is a divalent linker selected from the group consisting of: —NR y —, —N(R y )C(O)—, —C(O)NR y —, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO 2 —, —C(═S)—, —C(═NR y )—, —N═N—; a polyether; a C 3 to C 8 substituted or unsubstituted carbocycle; and a C 1 to C 8 substituted or unsubstituted heterocycle;
m′ is 0 or an integer from 1 to 4, inclusive; and
q is 0 or an integer from 1 to 4, inclusive.

2. The process of claim 1 , wherein a rate or time of addition of the catalyst replacement component is based on a rate of depletion of one or both of the Lewis acid

Assignees

• Novomer Inc

Inventors

• Farmer Jay J
• Galebach Peter
• Sherry Kyle
• Sookraj Sadesh H

Classifications

• C07D305/12 Primary

  Beta-lactones · CPC title

• C07C67/37

  by reaction of ethers with carbon monoxide · CPC title

• B01J31/00

  Catalysts comprising hydrides, coordination complexes or organic compounds (catalyst compositions used only in polymerisation reactions C08 {; catalytic antibodies C12N9/0002}) · CPC title

• C07D307/60 Primary

  Two oxygen atoms, e.g. succinic anhydride · CPC title

• C07C69/67

  of saturated acids · CPC title