Silylated and N-silylated compound synthesis

Details Silylated and N-silylated compound synthesis Silylated and N-silylated compound synthesis

2001-03-26

2002-06-25

Vollano, Jean F. (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Silicon containing

C556S428000

Reexamination Certificate

active

06410767

ABSTRACT:

FIELD OF INVENTION
This invention relates to certain novel silanes and to the synthesis of silylated and N-silylated organic compounds therewith.
BACKGROUND OF THE INVENTION
Typical procedures for the synthesis of silylated and N-silylated bis and mono(cyclopentadienyl) and indenyl ligands involve the addition of Cl
2
Si(CH
3
)
2
during synthesis of monocyclopentadienyl compounds to the lithiated ligand precursor. These procedures are not cost effective due to a requirement for excess Cl
2
Si(CH
3
)
2
, the production of undesirable by-products, and a consequent need for expensive purification procedures.
DEFINITIONS
In this specification, the following expressions have the meanings set forth:
1. MsO means CH
3
O
3
S or
2. MsOH means CH
4
O
3
S or
3. TfO means CF
3
O
3
S or
4. TfOH means CHF
3
O
3
S or
5. Monocyclopentadienyl ligand means any ligand having the formulae C
5
H
X
R
y
, wherein:
X=0-5
y=0-5
R=any alkyl or aromatic group or combination thereof, and H or R can occupy any one or more of the positions 1 to 5 of the formula
For example, R may be an alkyl group having one to eight carbon atoms including but not limited to methyl, ethyl, propyl, isopropyl, butyl, tertbutyl, hexyl or octyl. Methyl is the preferred alkyl group. R, when an aromatic group, may be phenyl, xylyl, mesityl, naphthyl or fluorenyl.
6. Silylated monocyclopentadienyl ligand means any ligand having the formula (R
3
Si)
Z
C
5
H
X
R
y
, wherein C
5
H
X
R
y
is as defined in definition 5, Z=1-5 and R and R
y
are identical or different alkyl or aromatic groups.
7. N-silylated monocyclopentadienyl ligand means any ligand having the formula RNH(SiR
2
)C
5
H
X
R
y
, wherein C
5
H
X
R
y
is as defined in definition 5, and R and R
y
are identical or different alkyl or aromatic groups.
8. Silylated biscyclopentadienyl ligand means any ligand having the formula (C
5
H
X
R
y
)
2
SiR
2
, wherein C
5
H
X
R
y
and R
y
are as defined by definitions 6 and 7.
9. Silylated monoindenyl ligand means any ligand having the formula (R
3
Si) (C
9
H
X
R
y
) wherein
X=0-7
y=0-7
H or R can occupy any positions 1 to 7 and R
3
Si can occupy only position 3 of the formula
wherein R and R
y
are as defined by definitions 6 and 7.
10. N-silylated monoindenyl ligand means any ligand having the formula RNH(SiR
2
)C
9
H
X
R
y
, wherein R and R
y
are as defined by definitions 6 and 7. (C
9
H
X
R
y
) is as defined in definition 9 and wherein X=0-7 and y=0-7.
11. Silylated bisindenyl ligand means any ligand having the formula (R
2
Si)C
9
H
X
R
y
wherein R and R
y
are as defined in definitions 6 and 7; X=0-7 and y=0-7.
SUMMARY OF THE INVENTION
One aspect of the invention includes novel silanes having the Formula (I):
(CX
3
SO
3
)
2
SiR
2
  (I)
or the Formula (II):
in which X is H or F, each R in formula (I) may be the same or a different alkyl or aromatic group as defined by definition 5 with the proviso that when X is F in formula (I), R is not methyl, and R
1
is an alkyl or aromatic group which may be the same or different from R.
Another aspect of the invention is a method for the synthesis of silylated and N-silylated compounds having the Formula (III)
 Y
2
Si(R)
2
  (III)
or the Formula (IV)
in which Y is any organic group and in which R and R
1
are the same or different organic groups, preferably substituted or unsubstituted aliphatic or aryl groups as defined by definition
5
.
The invention includes methods for reacting organic alkali metallides having the formula YM, in which Y is any organic group and M is any alkali metal with a silane having the Formula (I) or Formula (II) wherein the product is a compound having the Formula (III) or Formula (IV).
A first step of such methods includes preparation of an organic alkali metallide. Methods for the preparation of such compounds are known. For example, any compound having a —CH group, preferably acidic, is reacted with an alkali metal alkyl having the formula R
3
M, in which R
3
may be any hydrocarbyl group and M may be lithium, potassium or sodium. M may also be a magnesium halide. N-butyl lithium or tert-butyl lithium are preferred RM compounds. The reaction is conducted in a non-interfering solvent, preferably diethyl ether or tetrahydrofuran, which may also include or be combined or mixed with a hydrocarbon such as toluene. The reaction mixture contains a desired alkali metallide.
In a second step, the alkali metallide product of the first step is optionally but not necessarily isolated from the first step reaction mixture and reacted with a silane having the Formula (I) or the Formula (II). Methods for such isolating such compounds are known.
In one aspect of the invention, the compound having —CH group is a C
5
-ring containing compound useful as an olefin polymerization catalyst ligand or as a precursor of such a ligand. Such ligands include but are not limited to substituted, unsubstituted, mono-, or bis- cyclopentadienyl, indenyl, naphthenyl and antracenyl ligands. These ligands may be hydrogenated. For example, such ligands include cyclopentadienes, bis-cyclopentadienes, indenes, bis-indenes, mono- and poly- alkyl, preferably methyl, substituted cyclopentadienes and indenes, such as tetraethyl cyclopentadiene and 2-methyl indene, 2-methyl-benzo(indene), bis-2-methyl-benzo(indene), dimethyl silane, substituted, unsubstituted and bis-phenanthrene, and cyclopentaphenanthrene which may be but need not be hydrogenated.
Another aspect of the invention may include a method which comprises combining a compound having the formula Q
1
-(Z)-Q
2
Li
2
and a compound having the formula R
1
3
SiO
3
R
2
in a non-interfering solvent wherein said compound having the formula Q
1
-(Z)-Q
2
Li reacts with the compound having the formula R
1
3
SiO
3
R
2
to produce a compound having the formula
R
1
3
SiQ
1
(Z)
x
Q
2
SiR
1
3
or
R
1
3
SiQ
1
where Q
1
=indene
or
R
1
3
SiQ
2
where Q
2
=cyclopentadiene
wherein R
1
and Q
1
and Q
2
each have 1 to 10 carbon atoms are the same or different aryl, preferably phenyl, and R
2
are identical or different alkyl groups.
Specifically, Q
1
and Q
2
(i) may be the same or different;
(ii) are preferably unsubstituted;
(iii) may be substituted at any position not occupied by linkage to (Z)
x
or to lithium and
(iv) Z is a linking group, preferably (CH
2
)
y
in which y is 1 to 6 or Si(R
2
) wherein R
2
is a 1 to 6 carbon atom alkyl group.
Useful Q
1
and Q
2
substituents include one to six carbon atom alkyl, preferably methyl, groups; halogens, preferably chorine, fluorine or bromine, and substituents which form rings with two Q
1
or Q
2
carbon atoms.
Compounds having the formula Q
1
(Z) Q
2
Li are prepared in known manner by reacting a compound of formula Q
1
(Z)
x
Q
2
with an alkyl lithium compound, preferably n-butyl or t-butyl lithium in a non-interfering solvent, preferably ether or tetrahydrofuran. The lithiation reaction is appropriately conducted at a temperature of from about −80° C. to about 40° C.
The reaction mixture which contains lithiated Q
1
-(X)
x
Q
2
may be combined directly with R
1
3
SiO
3
SR
2
to yield R
1
3
SiQ
1
(X)
x
Q
2
SiR
3
. The reaction proceeds to substantial completion in about thirty minutes at room temperature. See Example 8. Alternatively, the lithium salt may be isolated prior to reaction with R
1
3
SiO
3
SR
2
.
DETAILED DESCRIPTION OF THE INVENTION
The Formula (I) silanes may be prepared by reacting a compound of the formula R
1
SO
3
H, in which R
1
is any straight or branched chain alkyl group preferably having one to eight carbon atoms, with a compound of the formula X
2
SiQ
2
, in which X and Q are as defined.
The synthesis of one Formula (I) silane is illustrated by Equation 1:
RT=Room Temperature.
The novel Formula (II) silanes are synthesized by reacting RSO
3
H with a compound having the formula (YNH)
2
SiQ
2
, in which R and Q are as defined, and Y is an alkyl group which may be the same as or different from Q. See Equation 2:


REFERENCES:
CA:125:59306 abs of Z Natu

Affiliated with

Also associated with

Rating

Silylated and N-silylated compound synthesis does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Silylated and N-silylated compound synthesis, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Silylated and N-silylated compound synthesis will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2957624