Method for preparation of cyano compounds of the 13th group with a lewis acid

Patent metadata

Field	Value
Publication number	US-9458180-B2
Application number	US-201415027008-A
Country	US
Kind code	B2
Filing date	Sep 23, 2014
Priority date	Nov 11, 2013
Publication date	Oct 4, 2016
Grant date	Oct 4, 2016

Abstract

The invention discloses a method for preparation of cyano compounds of the 13th group of the periodic table with 1, 2, 3 or 4 cyano residues, represented by formula (I): [Cat n+ ][Z 1 F 4-m (CN) m ) − ] n by a reaction of [(Z 1 F 4 ) − ] with trimethylsilylcyanide in the presence of a Lewis acid and in the presence of the cation Cat n+ ; Cat 2+ is a cation, Z 1 is B, Al, Ga, In or Tl, m is 1, 2, 3 or 4 and n is 1, 2, 3 or 4.

First claim

The invention claimed is:

1. A method for the preparation of a compound of formula (I);
[Cat n+ ][(Z 1 F 4-m (CN) m ) − ] n   (I)

the method comprises a step (St1);
step (St1) comprises a reaction (Rea1), wherein a compound of formula (A1) is reacted with trimethylsilylcyanide in the presence of CATLEWISACID;
[Cat n+] [(Z 1 F 4 ) − ] n   (A1)

CATLEWISACID is a catalyst CAT;
CAT is selected from the group consisting of [(CH 3 ) 3 SiFSi(CH 3 ) 3 ][ANIO], Q1(R27) 3 , guanidinium[ANIO], (R26) 3 C[ANIO], adamantyl[ANIO], [(R24) 3 O][ANIO], [(R25) 3 Si][ANIO], Q2(R36)(R28) 3 , Q3(R29) 3 , Q4(R30) 5 , Q5(R32) 3 , Q6(R33) 2 , Q8(R34) 2 , Q9(R35) 3 , Q10(R37) 2 , zeolite and mixtures thereof;
ANIO is selected from the group consisting of [P(R40) 6-m1 (R41) m1 ] − , [B(R42) 4-m2 (R43) m2 ] − , F − , Cl − , Br − , I − , CN − and SCN − ;
R40 and R41 are identical of different in independently from each other selected from the group consisting of CN, SCN, F, Cl, Br and I;
m1 is 0, 1, 2, 3, 4 or 5;
R42 and R43 are identical of different in independently from each other selected from the group consisting of C 6 F 5 , CN, SCN, F, Cl, Br and I;
m2 is 0, 1, 2 or 3;
Q1 is selected from the group consisting of B, Al and Ga;
R27 is selected from the group consisting of C 1-10 alkoxy, halogen, C 1-10 alkyl, CN, SCN and C 6 F 5 ;
R24 is C 1-10 alkyl;
R25 is C 1-10 alkyl;
R26 is selected from the group consisting of CN, SCN, Ph and C 1-10 alkyl;
Q2 is selected from the group consisting of Si and Ti;
R28 and R36 are identical or different and independently from each other selected from the group consisting of C 1-10 alkoxy, halogen, C 1-10 alkyl, CN, SCN and C 6 F 5 ;
Q3 is selected from the group consisting of P, Sb and Bi;
R29 is selected from the group consisting of C 1-10 alkoxy, halogen, CN, SCN, C 1-10 alkyl and C 6 F 5 ;
Q4 is selected from the group consisting of P, Sb and Nb;
R30 is selected from the group consisting of C 1-10 alkoxy, halogen, CN, SCN, C 1-10 alkyl and C 6 F 5 ;
Q5 is selected from the group consisting of Cr and Fe;
R32 is selected from the group consisting of halogen, CN and SCN;
Q6 is selected from the group consisting of Mn, Fe, Pd and Pt;
R33 is selected from the group consisting of halogen, CN and SCN;
Q8 is selected from the group consisting of Cu, Zn, Cd and Hg;
R34 is selected from the group consisting of halogen, CN, and SCN;
Q9 Sc or Ln;
R35 is selected from the group consisting of halogen, CN, and SCN;
Q10 Ca;
R37 is halogen;
Z 1 is selected from the group consisting of B, Al, Ga, In and Tl;
m is 1, 2, 3 or 4;
n is 1, 2, 3 or 4;
Cat n+ is selected from the group consisting of inorganic cation CatINORG n+ and organic cation CatORG n+ ;
CatINORG n+ is a cation selected from the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 11., 12., 13., 14., 15., or 16. group of the periodic table, or is a cation from the lanthanides or is a cation from the actinides or is NH 4 + ;
CatORG n+ is selected from the group consisting of CatORG-A + , CatORG-B + , CatORG-C + , [(CH 3 ) 3 SiFSi(CH 3 ) 3 ] + , Ph 3 C + , guanidinium and (H 2 (R18)N-R16-N(R19)H 2 ) 2+ ;
CatORG-A + is (WR2R3R4R5) + ,
wherein
W is a nitrogen or phosphorus; and
(i) R2, R3, R4 and R5 are identical or different and independently from each other selected from the group consisting of H, C 1-20 alkyl, C 1-20 perfluoroalkyl, C 3-10 cycloalkyl and C 6-10 aryl, with the proviso, that at least one of the residues R2, R3, R4 and R5 is not H; or
(ii) R2 and R3 together are a hydrocarbon chain and form together with W a 5- to 7-membered saturated or unsaturated heterocyclic ring,
R4 and R5 are identical or different and independently from each other selected from the group consisting of H, C 1-20 alkyl, C 1-20 perfluoroalkyl, C 3-10 cycloalkyl and C 6-10 aryl; or
(iii) R2 and R3 together are a hydrocarbon chain and form together with W, and R4 and R5 together are a hydrocarbon chain and form together with W, independently from each other, 5- to 7-membered saturated or unsaturated heterocyclic rings;
CatORG-B + is (XR6R7R8) + ,
wherein
X is nitrogen,
R6 and R7 together are a hydrocarbon chain and form together with X a 5- to 7-membered unsaturated heterocyclic ring in which X is connected by a single bond and a double bond to R6 and R7 respectively,
R8 is selected from the group consisting of H, C 1-20 alkyl, C 2-8 alkenyl, C 1-20 perfluoroalkyl, C 3-10 cycloalkyl or C 6-10 aryl;
CatORG-C + is (YR9R10R11) + ,
wherein
Y is sulphur;
(i) R9, R10 and R11 are identical or different and independently from each other selected from the group consisting of H, C 1-20 alkyl, C 1-20 perfluoroalkyl, C 3-10 cycloalkyl and C 6-10 aryl; or
(ii) R9 and R10 together are a hydrocarbon chain and form together with Y a 5- to 7-membered saturated or unsaturated ring,
R11 is selected from the group consisting of H, C 1-20 alkyl, C 1-20 perfluoroalkyl, C 3-10 cycloalkyl and C 6-10 aryl;
the residues R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 are, independently from each other, unsubstituted or, where applicable, substituted by 1, 2, 3, 4, 5 or 6 substituents selected from the group consisting of C 1-4 alkyl, C 3-10 cycloalkyl, C 2-8 alkenyl, phenyl, benzyl, halogen, cyano and C 1-4 alkoxy;
in any of said hydrocarbon chains formed by R2 and R3, by R4 and R5, by R6 and R7, by R9 and R10, 1 or 2 carbon atoms of said hydrocarbon chains can be exchanged for 1 or 2 heteroatoms respectively, said one or two heteroatoms being selected from the group consisting of O, N and S; in case of an exchange for N, this N is unsubstituted or substituted by a residue selected from the group consisting of C 1-8 alkyl, C 3-10 cycloalkyl, C 2-8 alkenyl and C 1-8 perfluoroalkyl;
R16 is selected from the group consisting of C 2-8 alkylen, C 3-8 cycloalkylen, phenylen, C(H)(phenyl), R17(—O-R17) n1 ;
R17 is selected from the group consisting of CH 2 —CH 2 , CH 2 —CH 2 —CH 2 , CH 2 —C(H)(CH 3 )—CH 2 , CH 2 —CH 2 —C(H)(CH 3 ) and CH 2 —CH 2 —CH 2 —CH 2 ;
R18 and R19 are identical or different and independently from each other selected from the group consisting of H, C 1-8 alkyl, C 3-8 cycloalkyl, phenyl and benzyl;
n1 is an integer from 1 to 20.

2. The method according to claim 1 , wherein
Z 1 is B.

3. The method according to claim 1 , wherein
n is 1 or 2.

4. The method according to claim 1 , wherein
m is 2, 3 or 4.

5. The method according to claim 1 , wherein
m is 3 or 4.

6. The method according to claim 1 , wherein
CatINORG n+ is a cation selected from the 1., 2., 3., 4., 5., 6., 7., 8., 9., 10., 11., 12., 13., 14. or 15. group of the periodic table or is a cation from the lanthanides or is NH 4 + .

7. The method according to claim 1 , wherein
CatORG n+ is selected from the group consisting of ammonium, phosphonium, sulfonium, pyrrolidinium, pyrrolinium, pyrrolium, pyrazolium, pyrazolinium, imidazolium, imidazolinium, triazolium, oxazolium, thiazolium, piperidinium, piperazinium, morpholinium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1,3-dioxolium, pyrylium, thiopyrylium, quinoxalinium, indolinium, indolium, [(CH 3 ) 3 SiFSi(CH 3 ) 3 ] + , Ph 3 C + , and mixtures thereof.

8. The method according to claim 1 , wherein
CatORG n+ is selected from the group consisting of

[N(R20)(R21)(R22)R23] + , [P(R20)(R21)(R22)R23] + , [(CH 3 ) 3 SiFSi(CH 3 ) 3 ] + , Ph 3 C + , and mixtures thereof;
wherein
R20, R21, R23 are identical or different and independently from each other selected from the group consisting of H, C 1-20 alkyl, C 3-10 cycloalkyl and allyl;
R22 is C 1

Assignees

• Lonza Ag

Inventors

• Sievert Katharina
• Schulz Axel
• Harloff Jorg
• Ellinger Stefan
• Taeschler Christoph
• Zur Taeschler Cornelia

Classifications

• B01J31/0287

  containing atoms other than nitrogen as cationic centre · CPC title

• C07D233/58 Primary

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms · CPC title

• B01J29/7049

  containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead · CPC title

• B01J27/125

  with scandium, yttrium, aluminium, gallium, indium or thallium · CPC title

• C07F5/027 Primary

  Organoboranes and organoborohydrides · CPC title