Method and mixture to form functionalized cyclic compounds

Patent metadata

Field	Value
Publication number	US-11053189-B2
Application number	US-201916362709-A
Country	US
Kind code	B2
Filing date	Mar 25, 2019
Priority date	Mar 25, 2019
Publication date	Jul 6, 2021
Grant date	Jul 6, 2021

Abstract

A method for producing a homocyclic or heterocyclic compound includes reacting a compound of formula (I) with a compound of formula (II) in presence of a base:

In formula (I), B is an unsaturated moiety selected from substituted or unsubstituted vinylene, ethynylene, aryleneethynylene, substituted or unsubstituted arylenevinylene, and a combination thereof, the vinylene or arylenevinylene has n (=0, 1 or 2) substituent(s) R 2 , G is an electron-withdrawing group, R 1 is hydrogen or a substituent, and two of R 1 , R 2 and G may joint together to form a ring. In formula (II), R 3 and R 4 are independently hydrogen or a substituent, R 5 is an electron-withdrawing group, and two of R 3 , R 4 and R 5 may joint together to form a ring. The conjugate acid of the base has a pK a in the range of 1 to 15.

First claim

What is claimed is:

1. A method for producing a cyclic compound, comprising reacting a compound of formula (I) with a compound of formula (II) in presence of a base,

wherein the cyclic compound has an unsaturated five-membered carbon ring formed by the reaction, and
in formula (I),
B is an unsaturated moiety selected from the group consisting of substituted or unsubstituted vinylene, ethynylene, aryleneethynylene, substituted or unsubstituted arylenevinylene, and a combination thereof, wherein the vinylene or arylenevinylene has n substituent(s) R 2 independently selected from the group consisting of deuterium, substituted and unsubstituted alkyl, alkenyl, alkynyl, alkenynyl, aryl, alkylaryl, arylalkyl, allyl, benzyl, cycloalkyl, cycloalkenyl, cycloalkynyl, cycloalkenynyl, alkanoyl, aryloyl, alkylsilyl, arylsilyl, alkoxysilyl, aryloxysilyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclic ring, heteroaromatic ring, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, ester derivatives, amide derivatives and metal salt derivatives of phosphonic acid group, phosphinic acid group, boric acid group, carboxylic acid group, sulfinic acid group, sulfonic acid group, sulfamic acid group and amino acid group, aliphatic moieties having a repeating unit of —(OCH 2 CH 2 ) q OCH 3 , —(OCH 2 CH(CH 3 )) q OCH 3 —(CH 2 ) q CF 3 , —(CF 2 ) q CF 3 or —(CH 2 ) q CH 3 , in which q=1, aliphatic chains having a moiety of (OR 18 ) r OR 19 , in which R 18 is a divalent C 1-7 alkylene moiety, R 19 is C 1-20 alkyl and 1≤r≤50, and substituent groups obtained by further substituting the above mentioned substituent groups with ester group, amino acid group, halo, epoxy group, amino, amido, acyl, organosilyl, organotin, organogermyl, nitro, alkoxy, aryloxy, alkyl, aryl, heteroaryl, alkylthio, heteroarylthio, arylthiol, or an ester derivative, an amide derivative or a metal salt derivative of phosphonic acid group, phosphinic acid group, boric acid group, carboxylic acid group, sulfinic acid group, sulfonic acid group, sulfamic acid group or amino acid group, n is 0, 1 or 2, and when n is 2, the two R 2 may be the same or different, and may joint together to form a ring;
G is an electron-withdrawing group selected from the group consisting of oxygen-containing electron-withdrawing groups, nitrogen-containing electron-withdrawing groups, sulfur-containing electron-withdrawing groups, phosphorous-containing electron-withdrawing groups, electron-withdrawing aromatic groups, electron-withdrawing heteroaromatic groups, halogen-substituted alkyl groups, and halogen atoms;
R 1 is hydrogen, or deuterium, or a substituent that is less electron-withdrawing than the electron-withdrawing group G, or unsubstituted alkyl, alkenyl, alkynyl, alkenynyl, aryl, alkylaryl, arylalkyl, allyl, benzyl, cycloalkyl, cycloalkenyl, cycloalkynyl, cycloalkenynyl, alkylsilyl, arylsilyl, alkoxysilyl or aryloxysilyl, or a substituent obtained by substituting any of the above unsubstituted groups with epoxy, amino, organosilyl, organotin, organogermyl, alkoxy, aryloxy, alkyl, aryl, heteroaryl, alkylthio, heteroarylthio or arylthio; and
two of R 1 , R 2 and G may joint together to form a ring;

in formula (II),
each of R 3 and R 4 is independently hydrogen or a substituent selected from the group from which R 2 is selected, wherein R 3 and R 4 are the same or different;
R 5 is an electron-withdrawing group selected from the group consisting of oxygen-containing electron-withdrawing groups, nitrogen-containing electron-withdrawing groups, sulfur-containing electron-withdrawing groups, phosphorous-containing electron-withdrawing groups, electron-withdrawing aromatic groups, electron-withdrawing heteroaromatic groups, halogen-substituted alkyl groups, and halogen atoms; and
two of R 3 , R 4 and R 5 may joint together to form a ring; and

a conjugate acid of the base has a pK a in a range of 1 to 15, wherein the base is selected from the group consisting of bases containing carbonate anion, bases containing bicarbonate anion, nitrogen-containing bases, and fluoride containing bases.

2. The method of claim 1 , wherein the base comprises a fluoride ion.

3. The method of claim 1 , wherein the reaction is carried out in an aprotic solvent.

4. The method of claim 1 , wherein the reaction is carried out in a solvent having a dielectric constant of at least 6.

5. The method of claim 1 , wherein the reaction is carried out in an anhydrous solvent.

6. The method of claim 1 , wherein the reaction is stirred at a temperature comprised in a range of 0° C. to 45° C.

7. A reaction mixture, comprising a compound of formula (I), a compound of formula (II), and a base,

wherein in formula (I),
B is an unsaturated moiety selected from the group consisting of substituted or unsubstituted vinylene, ethynylene, aryleneethynylene, substituted or unsubstituted arylenevinylene, and a combination thereof, wherein the vinylene or arylenevinylene has n substituent(s) R 2 independently selected from the group consisting of deuterium, substituted and unsubstituted alkyl, alkenyl, alkynyl, alkenynyl, aryl, alkylaryl, arylalkyl, allyl, benzyl, cycloalkyl, cycloalkenyl, cycloalkynyl, cycloalkenynyl, alkanoyl, aryloyl, alkylsilyl, arylsilyl, alkoxysilyl, aryloxysilyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclic ring, heteroaromatic ring, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, ester derivatives, amide derivatives and metal salt derivatives of phosphonic acid group, phosphinic acid group, boric acid group, carboxylic acid group, sulfinic acid group, sulfonic acid group, sulfamic acid group and amino acid group, aliphatic moieties having a repeating unit of —(OCH 2 CH 2 ) q OCH 3 , —(OCH 2 CH(CH 3 )) q OCH 3 —(CH 2 ) q CF 3 , —(CF 2 ) q CF 3 or —(CH 2 ) q CH 3 , in which q=1, aliphatic chains having a moiety of (OR 18 ) r OR 19 , in which R 18 is a divalent C 1-7 alkylene moiety, R 19 is C 1-20 alkyl and 1≤r≤50, and substituent groups obtained by further substituting the above mentioned substituent groups with ester group, amino acid group, halo, epoxy group, amino, amido, acyl, organosilyl, organotin, organogermyl, nitro, alkoxy, aryloxy, alkyl, aryl, heteroaryl, alkylthio, heteroarylthio, arylthiol, or an ester derivative, an amide derivative or a metal salt derivative of phosphonic acid group, phosphinic acid group, boric acid group, carboxylic acid group, sulfinic acid group, sulfonic acid group, sulfamic acid group or amino acid group, n is 0, 1 or 2, and when n is 2, the two R 2 may be the same or different, and may joint together to form a ring;
G is an electron-withdrawing group selected from the group consisting of oxygen-containing electron-withdrawing groups, nitrogen-containing electron-withdrawing groups, sulfur-containing electron-withdrawing groups, phosphorous-containing electron-withdrawing groups, electron-withdrawing aromatic groups, electron-withdrawing heteroaromatic groups, halogen-substituted alkyl groups, and halogen atoms;
R 1 is hydrogen, or deuterium, or a substituent that is less electron-withdrawing than the electron-withdrawing group G, or unsubstituted alkyl, alkenyl, alkynyl, alkenynyl, aryl, alkylaryl, arylalkyl, allyl, benzyl, cycloalkyl, cycloalkenyl, cycloalkynyl, cycloalkenynyl, alkylsilyl, arylsilyl, alkoxysilyl or aryloxysily, or a substituent obtained by substituting any of the above unsubstituted groups with epoxy, amino, organosilyl, organotin, organogermyl, alkoxy, aryloxy, alkyl, aryl, heteroaryl, alkylthio, heteroarylthio or arylthio; and
two of R 1 , R 2 an

Assignees

• Univ Nat Tsing Hua

Inventors

• Han Chien-Chung
• Alishetty Suman

Classifications

• C07C249/04

  of oximes · CPC title

• C07D307/68 Primary

  Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen · CPC title

• C07C2602/10

  the other ring being six-membered, e.g. tetraline · CPC title

• C07C253/02

  by reaction of nitrogen oxide with organic compounds · CPC title

• C07C233/57

  having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings · CPC title