CA1144533A - Procedure for the preparation of organolithium compounds together with lithium hydride - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A catalytic system is provided for the lithiation of .alpha. -olefins and .alpha.,.omega.-diolefins with concurrent production of lithium hydride. The catalysts include oxygen and sulfur containing organic compounds and polycyclic aromatics which can be combined with alkali metals and/or transition metal compounds.
High yields of pure and stereospecific lithiated olefins are obtainable.

Description

1 ¦ FIELD OF THE INVENTION

2 I .
(3 ¦ The present invention relates to a catalyst system for 4 ¦ the preparation of organolithium compounds from lithium and olefins with concurrent production of an equimolar amount of 6 lithium hydride, ,' 10 11 The conventional technical method of producing organo-12 lithium compounds (Kirk-Othmer, "Enc Chem. Techn.", Vol 12, 13 p. 547, 19~7) is based on the reaction of lithium metal with 14 organic halogen compounds, in which organolithium compounds as well as l~thium halides are produced:

17 RX + 2 Li- ~ RLi + LiX (1) 18 X = Cl, Br, I
19 Allyllithium and benzyllithium compounds may among others be produced by the splitting of the corresponding ether derivative 21 or acyloxy derivative with lithium metal (J. A. Katzen-ellenbogen 22 R. S. Lenox, J. Org. Chem., 38, 326, 1973; U Schollko~f in 23 "Methoden der Organischen Chemie", Houben-Weyl, XIII/l, P. 161;
24 J. J. Eisch, A. M. 3acobs, J. Org. Chem 28, 2145, 1963):
ROR' + 2Li > R-Li + R'OLi (2) 26 R = allyl, benzyl 27 R'- phenyl, mesitoyl 29 From the organolithium compounds so produced, numerous I ot r orcanolithiu~, compounds may be obtsined b~ means of .

11~4533 1 1 metal-H exchange:

43 ~ ~-Li + R'H , R-H + R'-Li (3) 5 1 or by means of metal-halogen exchange (D. Seebach. K.-H. Geiss 6 1 in "New Applications of Organometallic Reagents in Organic 7 ¦ Synthesis", p.l, Elsevier, 1976):

8 ¦ R-Li + R'-X~ R'-Li + R-X ~4) 9 ¦ X = Cl, Br, I
.' 101 . ,.
11 1 Only in exceptional cases had it heretofore been possible to 12 ¦ synthesize organolithium compounds directly from lithium metal 13 ¦ and hydrocarbons. Thus, for instance, l-alkines (H. Ogura, 14 ¦ H. Takashi, Synth. Commun., 3 135, 1973), trip~enylmethane or acenaphtylene (B, J. Wakefield, "The Chemistry of Organolithiu 16 Compounds", p. 70, Pergamon Press, 1974) may be lithiated with 17 metallic lithium. According to D, L. Skinner et al (J. Org.
lB Chem.,32, 105, 1967) lithium reacts with 1-alkenes in the 19 absence of a solvent to produce l-alkinyllithium compounds and lithium hydride.:
21 RCH=CH2 + 4 Li ~ RC_C-Li ~ 3 LiH (5) 22 whereby l-lithio-l-alkenes are produced as byproducts of the 23 reaction, at very small yields. In the presence of tetrahydro-24 furan (THF) l-lithio -l-hexene was obtained from lithium and l-hexene at boiling temperatures, at 9% yield.

27 A procedure for the preparation of organolithium compounds 28 from lithium and ethylene in dimethoxymethane or THF in the 29 presence of biphenyl and, if the ca~e, naphLha~ene ~as recently 30 ~1 mzde o~n (V P~autenstrauch of Firmenich 5 A., Geneva, Swiss .
, . Patent 585, 760, May 20, 1974; V. Rautenstrauch, Angew, Chem., 2 ¦ 87, 254, 1975). The yields of organolithium compounds according

- 3 j to these procedures are at very low levels. Since the reaction

4 I products furthermore occur in the form of a mlxture of vinyl-

5 ¦ lithium and 1,4-dilithiobutane, this procedure hardly seems

6 I suitable for technical purposes.

7 I

8 1 SUMMARY OF THE INVENTION

9 l

10 ¦ The present invention provides a catalyst comprising

11 ¦ a composition of the formula

12 ¦ /A B \

4 ¦ ~ \D~ ~ ~ Men(L)p~L )q (*

16 ¦ wherein A and B are sulfur or oxygen 17 ¦ G is a carbon atom bonded to 18 ¦ a radical Rl l9 ¦ D is a carbon atom bonded to a 20 ¦ radical R2 and there is a double bond 21 ¦ between the carbon atom of G and of D;
22 ¦ E is carbon 23 ¦ F is oxygen, 24 ¦ sulfur, 26 = CR3 - CR4, or 23 = CR3 - CR4 Me is an alkaline metal n is an integer from 2 to 20;
~ L and L' are mono or poly-functional i . A

; ll 11~4S33 .
1 ~ ethers or amines;
2 ¦ p and q are integers from O to 4;

4 ~ Rl, R2, R3 and R are-independently hydrogen, .
5 ¦ alkyl, cycloalkyl, 6 ¦ aralkyl or aryl groups 7 ¦ and/or two or more of such groups are closed into ¦ an aliphatic or aromatic ring system; and 8 ~ .

10 ¦ a metal compound of transition metals from group Ib, IIb, 11 ¦ IVb, Vb, VIb, VIIb and VIII of the transition metals of the 12 ¦ periodic system.

13 ¦ Preferably Rl, R2, R3, R4 have less than about 20

14 ¦ carbon atoms. Alkyl groups include methyl, ethyl, isopropyl,

15 ¦ n d~cyl, stearyl.

I : Cycloalkyl groups include cyclopentyl, cyclohexyl, 18 ¦ decahydronaphthyi.

20 I .
l Aralkyl groups include benzyl, phenylethyl and 21 ¦ naphthyl methyl. Aryl groups include pXenyl, tolyl, xylyl, 22 ¦ naphthyl, penanthryl and diphenyl~

~wo groups closed in to an aliphatic ring system include propylene and butylene groups.

28 Two ~roups closed into an aromatic ring system include benzo and naphtho groups.

11~4533 l ¦ Preferably the ratio of moles of the composition of the 2 ~ formula (*) to the moles of transition compound is in the range 4 I from about l:lO to lO:l.

5 ¦ In the formulas (*) above, (**) and (***) below, certain 6 I single bonding lines may represent double bonds and there 7 ¦ can also be a bond between A and B when both A and B are 8 ¦ ¦ sulfur lO I Preferred catalysts of the present invention includ 6 tbose wherein the composition has the fol1Owing formula:

4 . ~ ~ C / ~X~ Men(Llp(L ) 18 and ~herein X is sulfur or oxygen.
21 A more preferred composition has the formula ( I - S

and the metal compound is cuprous chloride of ferric chloride.

3 ¦ Another preferred catalyst has a composition of the 4 ¦ formula 1~ ~ ~1~ \'C ~C~ R~M~ L)p~L ~q 11 I wherein X is sulfur or oxygen.-13 More preferred are catalysts of the formula (II) 14 wherein X is sulfur, R = R is C6H5, and

16 R2 = R3 is hydrogen and

17 Me is lithium and

18 wherein the metal compound is zinc chloride, or palladium

19 chloride or wherein X is sulfur 221 Rl ~ R3 is C6H5, .

22 R = R4 is hydrogen and 23 Me is lLthium, and 24 wherein the metal compound is cupric chloride.

26 The metal compound can be of a metal selected from the 27 groups consisting of copper, gold, zinc, cadmium, titanium, 28 zirconium, vanadium, niobium, tantalum, chromium, molybdenum, 29 tungsten, manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.
. .

. ~
1 I Preferred metal compounds are of a metal selected from 2 ¦ the group consisting of copper, iron, zinc, palladium, platinum 3 ¦and rhodium.
4 l 5 ¦ Preferred metal compcunds include halides and organic 6 ¦complexes such as acetylacetonites, more preferred are transition 7 ¦metal chlorides.

9 ¦ Exemplary metal compounds include compounds selected from the group consisting of 11 zinc chloride, 12 iron (III) chloride 13 copper (I) chloride .
14 copper .(II) chloride molybdenum (VI) chloride 16 titanium (IV) chloride 17 chromium (III) chloride 18 molybdenum (V) chloride 19 managanese (II) chloride ~.
cobalt (II) chloride 21 nickel (II) chloride 22 nickel (II) acetylacetonate 23 rhodium (III) chloride 24 . platinum (II) chloride palladium (II) chloride 26 . The metal compound is preferably an anhydrous metal 2B compound.
29 In one aspect, the present invention provides a 30 l cata t co=position of metal complexes comprising l ¦ a polycyclic aromatic compound;
2 ¦ an alkali metal; and 3 1 a metal compound of transition metals 4 ¦ from group Ib, IIb, IVb, Vb, VIb, VIIb and 5 ¦ VIIIb of the periodic system.
, 61 7 ¦ The polycyclic aromatic compound has preferably from abou 8 ¦ 10 to 24 carbon atom. Typical aromatic compounds include ¦ naphthalene, lO ¦ anthracene, 11 ¦ phenanthrene, and 12 ¦ diphenyl 14 ¦ The alkaline metal can be lithium, sodium or 15 ¦ otassium and more preferred is lithium.
16 1 .

17 ¦ The present invention also provides a process for 18 ¦ reparation of organo lithium compounds and lithium hydride 19 ¦ comprising contacting lithium with ~ olefin or an a,~ -diolefin

20 ¦ in the presence of a catalyst comprising:

21 1

22 ¦ a metal organic composition of the formula

23

24 S ~ ~ (**) 1 wherein A and B are sulfur or oxygen, 2 G is carbon bonded to a radical Rl 3 D is carbon bonded to a radicàl R2, 4 and, if A and B are oxygen, also to a hydrogen atom, 6 E is carbon, 7 F.is a member of the group consisting of 8 oxygen, 9 sulfur, hydroxy where B is oxygen, .
11 O .
12 - CHR3 - CR4 where B is oxygen, 13 . 0 14 = CR3 - CR4 where B is sulfur, and 15 . -S
16 = CR3 = CR4 where B is sulfur 17 R , R2, R3, R4 represent hydrogen, 18 alkyl, cycloalkyl, aralkyl or 19 aryl groups and/or two or more .
of such groups are closed into an 21 aliphatic or aromatic ring system, 22 and 23 M* represents a metal compound of metals from groups 24 Ib, IIb, I~, Vb, VIb, VIIb, and VIIIb or the periodic system and/or a group Men (L)p (L')q 26 wherein Me is an alkali metal 27 n is an inte~er from 2 to 20;
2~ L and L' are monofunctional or polyfunctional 29 ethers or amines, and ~0 p and q are integers from 0 to 4;

1 ¦and/or a composition of metal complexes comprising polycyclie 2 ¦ aromatics, an alkali metal, and a metal compound of transition 3 ¦metals from group Ib, IIb, IVb, Vb, VIb, VIIb and VIIIb of the 4 ¦ periodic system.
5 l 6 ¦ If A and B are sulfur in formula (II) there can .
7 I be a bond between A and B and when 8 I F is = CR3 ~ CR4 there is a bond between B and 9 ¦ the sulfur atom of the -S group.

11 ~ -CR4 12 ¦ A preferred metal organic composi~ion employed in 13 ¦ the process has the formula 18 ~ ~ C / ~x~ Me~L)p(L )q (I~

2l9 I , - . ................ .,. . .... . , ' ., 21 ¦wherein X is sulfur or oxygen and more preferred are .
22 ~ catalysts with compositions of the formula

25 ~ ~ ~ ~ ) Lin ~ 2 Cu Cl 4~S33 .
I . ' -. .
2 land of the formula -~ L~n ~ Fe ~13 9 ¦ The metal organic composition can have the formula ',,'10 I . .

2 \~ ~'C I ~1M n( P q (Il) 16 1 .
17 ¦wherein X is sulfur or oxygen, and preferably 18 wherein X is sulfur, 19 ¦ R ' = R4 is phenyl, 2 0 I R - R is hydrogen and .
21 I Me is lithium, and 22 ¦wherein the metal compound is zinc chloride or palladium 23 I chloride or 24 ¦wherein X is sulfur 25 I Rl = R3 is phenyl

26 ¦ R2 = R4 is hydrogen, and

27 ¦ Me is lithium, and

28 ~herein the metal compound is cupric chloride.

29 I .
~0 ¦ The metal compound of the catalyst employed in the 11~4533 1 ~ proces~ can be the metal compound of a metal selected from the 2 ¦ ~roup consistin~ of copper, gold, zinc, cadmium, titanium, 3 I zirconium, vanadium, niobium, t~ntalu~, chromium, molybdenum, 4 tungsten, manganese, iron, cobalt, nickel, ruthenium, rhodium, 5 ¦ palladium, osmium iridium and platinum, and preferably 6 ¦ the metal compound is of a metal selected from the group consist-7 ¦ ing of copper, iron, zinc, palladium, platinum and rhodium.
8 .
9 Typical metal compounds include those selected from the group cor.sisting of 11 zinc chloride, 12 iron (III) chloride, .
13 copper (I) chloride, 14 copper (II) chloride, molybdenum (VI) chloride, 16 titanium (IV) chloride, 17 chromium (III) chloride, 18 molybdenum (V) chloride, 19 manganese (II) chloride, cobalt (II) chloride, 21 nickel (II) chloride, 22 nickel (II) acetylacetonate, 23 rhodium (III) chloride, 24 platinum (II) chloride and palladium (II) chloride.

27 Preferably the metal compound is an anhydrous metal 28 compound.

A sDlvent can be added to the lithium, to ~he J - or . q 4~33 -~
11 . . .

2 ¦ the ~ diolefin and/or to the catalyst.

4 ¦ The solvents include cyclic or an open-chain monoether 5 ¦or polyethers such as the tetrahydrofuran. The catalyst can be 6 ¦formed in situ, by contacting lithium with compounds of the gen-7 ¦eral formulae III and IV, or V, VI and VII
8 ~

10 I S S , o ~ S --~ S

13 ~ / l c~x ~1' C ~ ~0 Rl~ C ~C ~ ~n~

l6 III .... IV v ''19 .' 2~ S - S o O ' 22 ~ C C ~ ~ R4 1~ C`c~ ~ ~`CH~ C ~ 4 (VI) (VII) 26 wherein X is sulfur or oxygen and alternatively lithium is, contacted with compounds of the general formulae III, IV, V, 28 VI, or VII and with a metal compound of transition metals from 29 groups Ib, IIb, IVb, Vb, VI~, VIIb, and VIII of the periodic system.

1 jAlso lithium can be contacted with a catalyst consisting of 2 ¦isolated adducts between compounds III to VII, and 3 !metal compounds of transition metals from groups Ib, IIb, IVb;

S ~Vb, VIb, VIIb and VIIIb of the periodic system.
6 Prefarably a member of the group consisting of the 7 reaction products of the formulae .

.~o ~ vbS.2cuc, 16 . ' . `~ .
17 , ;' ' , ''''' .,' 20 C6 ~ 2 CuC12 and ~ ~ s . 2 reC13 ¦~
2232. ' .

224 is contacted with lithium.

26 In a further aspect of the invention lithium is contacted 27 with a catalyst, producted from a polycyclic aromatic compound 28 such as anthracene, naphthalene or biphenyl and a metal compound 29 of metals from subgroups I, II, IV, V, VI, VII and VIII of the

30 per ic system.

;-- 1` . 114g533' ' 1 j The contacting can be from about -100 C to ~ 100 C, 2 ¦- and is preferably from about -20C and ~50C. Preferably the partial pressures prevailing in the process are less than 4 about 100 bar. The ~-olefines include those of the general .
formula CH2=CHR , wherein R is H, alkyl, aryl, cycloalkyl 6 or aralkyl, and *he a,w diolefins lnclude those of the 7 formula CH2 = CH - (CHR)n ~ CH = CH2 8 wherein R is hydrogen, alkyl, aryl, cycloalkyl or araikyl and-9 n is an integer from 1 to 6.
., ' 10 11 In a further aspect of the invention, a process is 12 provided for preparation of a catalyst comprising contacting 14 an organic compound of the formula .
16 /A B ~
17 I I \ (***) 18 ~ ~ F

21 wherein A and B are sulfur or oxygen 22 G is a carbon atom bonded to 23 a radical Rl 24 . D is a carbon atom bonded to a 2~ radical R2 and there is a double bond 26 between the carbon atom of G and of D.
27 E is carbo~
28 ~ F ~s oxygen ~ I

4533 ` .

1 - CR3 - CR4, or 2= CR3 - CR4 . . .

4Rl, R2, R3 and R4 are independently hydrogen, alkyl, 5cycloalkyl, aralkyl or aryl groups 6 . a~dlor two or more of such groups are .
7 closed into an aliphatic or aromatic .
B ring system;

an alkaline metal; and 11 .. ,, .
12 mono or poly-functional .
l43 ethers or amines.

lS A metal compound of transition metals from groups Ib, 16 IIb, IVb, Vb, VIb, VIIb and VIII of the periodic system can 18 be added to the resulting composition.
19 . Preferred organic compounds in preparing the catalyst 20 include those of the formulas ~.

~6 / C~ X 1~ /C ~ 1 C ~ ~C ~ C ~ 4 4533 ` ~ .

3 R1~ C ~ ~ 4 _ C ~ C~ ,C ~ F4 6' 1 , 7 I VI VII ' 8 I . , 9 ¦ wherein X is sulfur or oxygen.
,,' 10 I , .
11 ¦DETAILED DESCRIPTION OF THE INVENTION
12' ¦INCLUDING'PRE~ERRED EM~ODIMENTS

14 ¦In accordance with the present invention, it was 15 ¦ surprisingly found that a-~olefins and ,~-diolefins can be 16 ¦ reacted,with metallic,lithium in the presence of appropriate i7 ¦ catalysts, and the reaction products include p~re and stereo-18 ¦specific organolithium compounds and lithium hydride. The 19 ¦ reaction between lithium and olefins is carried out for practical 20 ¦ reasons in solvent such as a cyclic or open-chain monoether or 21 ¦ polyether (preferably tetrahydrofuran, THF) at temperatures from 22 ¦ about -100 to +100C and,preferably from about -20C to +50C and 23 ¦ at partial pressures of preferably below 1 bar and at from about 1 24 ¦ to 100 bar pressure.

26 ¦ Accordingly, the invention relatés to a process 'for 27 ¦ production of organolithium compounds in addition to lithium 28 ¦ hydride, wherein lithium is contacted with a catalyst from the 2 9 ¦ following group:
., :
~

4S33 .

1 (a) an alkali-metal complex compound of the 2 general formulae I or II

4 l C C ~ \
6 ~R1~ ~ C / ~X¦ ~len~L~p~L )q B (I) '-'10 . 11 ~ C ~ ) 16 . II

18 wherein Me is an alkali metal, 19 X is sulfur or oxygen;
n is an integer from 2 to 20; . .
21 L and L' are monofunctional or polyfunctional ethers 22 or amines;
23 p and q are integers from 0 to 4;
24 Rl, R2, R3 and R4 are hydrogen, alkyl, cycloalkyl, aralkyl or aryl groups; and/or 26 where two or more of such groups are 27 closed into an aliphatic or aromatic 28 ring system; or 4S33 `
I
1 ¦ (b) a catalyst according to (a) in the presence of 2 ¦ . . a metal compound of transition metals from 3 ¦ group Ib, IIb, IVb, Vb, Vlb, VIIb, and VIII
4 ¦ of the periodic system; or . ¦ (c) a catalyst, produced from polycyclic aromatics 6 ¦ such as anthracene, naphthalene and biphenyl and 7 ¦ alkali metal in the presence of a metal compound 8 ¦ of transition metals from group Ib, IIb, IVb, Vb, 9 ¦ VIb, VIIb, and VIII of the periodic system; or , 10 (d) adducts between compounds of the general formulae 11 III to VII
12 . .
l3 ~ `O

18 III , ; IV V
l29 . . , . .
21 S - S~ O O
22p1~ C ~ C ~ ~C ~ ~ ~4 ~ C~H~ C~ c ~ R4 23 l2 1l3 l~ b3 26 VI _ VII
27 in which Rl, R2, R3 and-R4 have the meanings indicated 28 under (a), and transition-metal compounds of transition 29 metals from group Ib, Ilb, IVb, Vb, VIb, 'IIb and VIII of the periodic system.in a solvent with an ~-olefin -2(i-533 ~ `
.' I
l ¦or ~ diolefin. - .
2 I .
- 3-The catalysts mentioned above under (a) and their preparation are described in German Patent Disclosure Record S27 22 221.5.

7The invention furthermore relates to catalysts from 9(a) an alkali metal complex compound of the general lOformulae I or II .

13 . I X ~ \
4 ~Rl~ C/ ~X~ Men~L)p(L Iq 16 . .

l8 l .

22 ~ ~ ~ ~ C / ~ C~ ~ n~ .(L)p~LlI
23 Il _ .
24 . . ~
in which Me is an àlkali-metal; X is sulfur or oxygen; n is 26 an integer from.2 to 20; ~ and L' are monofunctional or poly-27 functional ethers or amines; p and g are integers from 0 to 28 4; Rl, R2, R3 and R4 are hydrogen, alkyl, cycloalkyl, aralkyl 29 or aryl groups and/or where two or more of such groups are closed into an aliphatic or aromatic ring system; and 533 - .

1 (b) metal compounds of transition metals from group Ib, 2 ~ IIb, IVb, Vb, VIb, VIIb, and Vlllb of the period 3- ¦ system or from S (c) complexes of polycyclic aromatics such as antracene, 6 ¦ naphthalene and biphenyl, and an alkali-metal 7 with 8 I .
(d) a metal compound of transition metals of group lB, Ilb, IVb, Vb, VIb, VIIb, and VIlIb of the 11 ¦ periodic system.
12 I .
13 Among the metals from the group Ib, IIb, IVb, Vb, VIb, 14 VIIb and VlIIb of the periodic system are included copper, gold, zinc, cadmium, titanium, zirconium vanadium,niobium, 16 tantalum, chromium, molybdenum, tungsten, manganese, iron, 17 cobalt, nickel, ruthenium, rhodium, palladium osmium, iridium 18 or platinum. Of these, we prefer copper, iron, zinc, palladium, 19 platinum and rhodium.
21 Examples for the monofunctional or polyfunctional ethers 22 or amines designated by an L or L', in general formulae I and II, 23 are as follows: Cyclic ethers such as tetrahydrofuran or 24 glycol ether, and amines such as tetramethylethylene diamine or morpholine. The monofunctional or polyfunctional ethers or 26 amines have preferably less than about 10 carbon atom. Catalyst 27 formation may also be carried out in a manner such that compounds 28 of the general formulae III, IV, V, VI, and VII -- which are 29 also described in German Patent Disclosure Record No. 27 22 221.5 -- are mixed with alkali metals, preferably , 533 .
.

l lithium, and, if appropriate, with a metal compound of metals from subgroups I, II, IV, V, VI, VII and VIII of 3 ¦ the periodic system, in an appropriate solvent; and, if 4 ¦ appropriate, in the presence of ~ -olefins or ~ diolefins.
A particularly active and selectively operating catalyst 6 ¦ system, in the sense of the present procedure, is produced, 7 1 if 2,5-diphenyl-1,6,6a-trithiapentalene (V, R1=R4=C6H5, 8 R2=R3=H) is converted in combination with zinc chloride I in the presence of ~ -olefines or ~ diolefins in THF
lO ¦ with lithium (see Examples 40 - 42).

.11 12 Finally, it is also possible to let isolatable adducts 13 ¦ between compounds of the general formulae III - VTI, listed 14 above under (d), and trasition-metal compounds of subgroups I, II, IV, V, VI, VII or VIII of the periodic system 16 I operate as catalysts on the lithium and olefin or diolefin.
17 ¦ Thus, for instance, iron (III) chloride, copper (I) chloride, 18 ¦ and copper (II) chloride, as well as molybdenum (V) chloride 19 ¦ form, with 1,2-dithiol-3-thiones or 1,6,6a-trithia-pentalenes, 2 : 1 adducts which may be used instead of 21 ¦ a mixture of both components to produce the catalystfi. By 22 ~ the same token, the complex ortho-chloropalladio-2,5-diphenyl-23 ! 1,6,6a-trithiapentalene(6) which can be produced from 24 ¦1 2,5-diphenyl-1,6,6a-trithiapentalene and PdCl2 yields with 25 1' lithium in THF an active catalyst for the lithiation of olefins:, ' . , ,~
27 i1 - .

- 22 a -~ ~ S
2 ¦ 5 6 ~ ~ ' ~dC12 __ HCl ~ .

C~ \ ( c ~ l6 llThe catalytic lithiation of ethylene.with the aid of 12the catalysts according to the inve~tion, in for instance .
13 THF, lead to vinylIithium and lithium hydride:

. Cat/THF
152 2 ~ CH2=CHLi + LiH (7) 17 IThe vinyllithium soluble in THF may be separated from .
l8 ¦ the insoluble lithium hydride and may be further used in l9 solution or isolated in crystalline form. Depending on the 20 I catalyst, the yields of vinyllithium range from 60 to ~ore than 21 70 % of the amount calculated according to (7).
22 l 23 In the catalytic lithiation of propene according to the 24 ¦, procedure of the invention, there are generally produced four 25 j, isomeric organolithium compounds: Trans-1-propenyllithium ~9)~
2~ ci~ ropen~llithium (10), isopropenyl~ithiu~i (11) and 27 ! allyllithium (12), in addition to lithium hydride:
2.
- _3 -Cat/THF
CH2=CI~CH3 + 2 Li -1 jf~; \

( }'`C=C~ 3 `C-C .3 `C-C' 3 C~2-~n 2,~ ~,iH

\ ~ 10 ~ 8) , The selectivity of this reaction in relation to the formation of individual isomers may be controlled through the selection of the catalysts. Thus, in the presence of catalysts produced with the u~e of iron, copper, cobalt or zinc compounds, trans-l-propenylithium 9 is produced at high selectivity. On the other hand, the catalytic lithiation of propene may be controlled by using palladium, platinum or rhodium compounds in a manner such that predominantly allYllithium 12 is produced. One catalyst tha~
operates in a particularly selective fashion in this sense was found to be the palladium complex (6), with the aid of ~:hich allyllithium may be obtained with a selectivity of 85-90%. In the example of lithiation of l-butene with this palladium complex as a catalyst it is shown that higher ~ -olefins may also be selectively lithiated in the allyl position. On the other hand, using catalysts produced with the utilization of zinc, iron or copper compounds,higher 1 alkenes such as l-butene, l-pentene, l-octene and l,7-octadiene may also be selectively lithiated in the trans -1 position. Thus, for instance, l-octene may be lithiated with the aid of above-mentioned catalyst from 2,5-diphenyl-1,6,6a-trlthiapentalene and ZnC12, with a selectivity of more than 96% in the l-trans position.

H R H R
C=C / + 2 Li Cat./Solv. ~ ~ C=C ~ ~ LiH (9 H / H ' Li H
R = CH3, C2H5, n-C3H7, n-C6H~ (CH2)n- etc-If appropriate, the trans-l-lithio-l-alkenes may be isolated in analytically pure crystalline form. By means of crystallization, the ratio of trans-l-lithio-l-alkene is generally raised. The present procedure thus permits a selective preparation of trans-l-alkenyl or allyllithium compounds from ~-olefins or diolefins and lithium.

In the catalytic lithiation of 1,4-pentadiene in the presence of the 4,5-benzodithiol-3-thione 2CuC12 complex there is produced a heretofore unknown organolithium compound with the following structure:

~ ~ 5 ~C~C12 1~ > <~ (9 The starting point materials for the preparation of organolithium compounds in accordance with the present inven-tion are preferably ~ - olefins and ~,~ olefins having up to about 40 carbon atoms. They include those ~14~533 Gf the general formulae CH2=C~R, in which R = H, alkyl, aryl, cycloalkyl or aralkyl; or diolefins of the general formulae CH2=CH-(C~R)"-CH=CH2, in which R has the same significance as above,and n = 1 - 6.

.

The catalytic lithiation of ~-olefins or ~,~ -diolefins in accordance with the invention represents a new method of preparation of organolithium compounds which cannot be produced in any other way or can only be produced with great difficulty.
In lieu of the expensive and often toxic as well as hard-to-procure organohalogen compounds, the present procedure uses commercially available olefins. Moreover, when the conventional method is used, one-half of the lithium that is used winds up as a lithium halide, and is thus lost for further conversion. The procedure according to the invention supplies, besides the organolithium compound,highly reactive and technically valuable lithium hydride.
The entire amount of lithium applied is converted into valuable lithium compounds.

The present procedure permits a regioselective or stereo-selective synthesis of organolithium compounds, providing the capability of controlling the reaction by the proper choice of the catalyst or the reaction conditions, in a manner such that, depending on the need, different organolithium compounds may be obtained from the same starting-poin~ olefin.

_ _ _ 1~4533 The organolithium compounds that can be prepared by the present procedure may be used as in~tiators for anionic polymerisations of mono- olefins or diolefins, or as reagents for the introduction of organic unsaturated groups, as well as for reduction in organic svnthesis.

The followin~ examples represent preferred embodiments of the present invention.

Exam~

All experiments for the preparation of organolithium compounds are carried out in a protective gas atmosphere, such as argon.

Example 1 ~ S _ S

1 (o 1~ ~ 5 Z CuC12J 13 For the preparation of the 4,5-benzo-1,2-dithiol-3 -thione ~
2CuC12- complex (13), 2.83 g (21.05 mMoles)of anhydrous copper(II) chloride are suspended in 100 ml of benzene, are added to 2.00 g (10.85 mMoles) of 4,5-benzo-1,2-dithiol-3-thione, and the mixture is stirred for 18 hours at room temperature. The suspension is filtered, the precipitate is washed with benzene and dried at 10 3 Torr. This yields 3.58 g (7~% of theoretical) of the complex 13.C7H4S3Cu2C14 (453.16);

, . . _ , . _ .
i 11~4S33 calc. C 18.55, l~ 0.89, S 21.22, Cu 28.04, Cl 31.29;
found C 17.50, H 1.00, S 20.90, Cu 27.60, Cl 32.70.

A solution of 1.40 g (3.09 mMoles) of complex 13 in 100 ml of absolute THF is saturated with propene tl bar) at 0C;
immediately thereafter, 5.07 g (0.73 Moles) of lithium sand is added to the solution in a propene atmosphere at 0C and under stirrlng (molar ratio 13:Li = 1:236).~fter a temporary temperature rise, the absorption of propene starts after 10-15 minutes; the rate of propene absorption can be measured with the aid of a gas burette connected to the reaction vessel.
During the propene absorption, the suspension is stirred, wlth propene pressure kept st 1.1-1.2 bar and temperature kept at 0C to+2C. The dark brown reaction mixture absorbs 6.0 liters of propene (1 bar, 20C) until it is saturated within 49 hours (68.5% of theoretical). The suspension is filtered at OOr~ the precipitate is washed with THF and dried at 0.2 Torr. This yields 4.41 g !'" ~ of lithium hYdride ~ixed with a little lithium (0.135g of the mixture yield with ~2 257 ml of gas (1 bar, 20 C), consisting of 13D (70~), D2 (19%) and H2 (11%). For the purpose of analyzing the organolithiu~
compound in the solution, an aliquot of the solution (8.0 ml of a total of 142.0 ml) is concentrated under vacuum (0 2 torr) and the solid residue is hydrolyzed. The amount of ~as produced thereby is 335.5 ml (1 bar, 20C) and consists of propene (84.9~), THF (4.6~), 332 (3.5%) and acetylene (1.4%). From the amount of -'8-1~4533 propene, ~qu.8 permits calculation of a yield in organolithium compounds LiC3135 of 57.7~. In order to determine the distribution of isomers, 58.0 ml of the solution ar~ concentrated under vacuum (0.2 torr), the residue is dissolved in 60 ml of ether, mixed at 0C w1th 18.9 9 (174 m~]oles)of trimethylchlorosilane, and the mixture is stirred 12 hours at 20C. Hydrolysis or processing and distillation produces, in addition .to hexamethyldisiloxane, 7.3 g of a mixture of the isomeric silanes(CH3)3SiC3H5 (B.P.
87-89C/760 torr), consisting of trans -l- propenyltrimethylsilane 74.5~, cis -l- propenyltrimethylsilanc 1.7%, isopropenyltrimethylsilarl -8.1%; and allyltrimethylsilane 15.3%.

.
In order to isolate the trans -l- propenyllithium (9), 74.0 ml of the solution are concentrated under vaccuum (0.2 torr) to 33.0 ml, added to 50 ml pentane, mixed for lO minutes and filtered. For the purpose of crystalizing (9~ the filtrate is kept for 3 hours at -40C and for 12 hours at -78C. The crystals of (9) are filtered at -78C, are wash~d three times with 40 ml of cold pentane each, dried for one-half hour at -30C, one-half hour at 0C and one hour at.20C under vacuum (0.2 torr). This yields 9.25 9 of the trans -l- propenyllithium-tetrahydrofuran adduct, in the form of light brown crystals (Li-.content 6.51; yields 45.6~ of th~oretical, referred to lithium). The l}3-NI~R spectrum of the product (80 M13z, 10 % in (C2D5)20;
'~= 3.39 ~ (H~), 3.78 m (~
Li K ~ 6.17 m (~), 8.10 m (~ , 8.~8 d H ~ ~ C13 ~ (HC~; J~2 = 21 Hz) (9) - 2q 11~4533 agrees with that of D. Seyferth and L.G. Vaughan (J. Organomet.
Chem.1,-201, 1963) prepared from trans-l-chloro-l-propene and lithium (9).

For further purification, 9.0 g o~ the raw material are re-crystalized from a mixture of 18 ml of THF and 32 ml of pentane, as described above. This yields 6.5 g trans-l- propenyllithium-tetrahydrofuran adduct, in the form of colorless crystals.
C3H5Li-C4H8O (M.W. = 120.0); calc. 5.78~ Li; found 5.75 Li. The conversion of 6.0 g (49.7 mMole) of this product with trimethyl-chlorosilane, as described above, yields 5.43 g of (CH3)3SiC3H5 with the following composition: trans -l- propenyltrimethylsilane, 93.4%; cis-l- propenyltrimethylsilane, 0.4%; isopropenyltrimethyl-silane, 1.3%; and allyltrimethylsilane, 4.9~.

Example 2 ~ - S

~~~S

(3a) `~
.
A solution of 0.90 g (4.9 mMole) of 4.5-benzo-1,2-dithiol-3-thione (BDT) (3a) and 1.63 g (9.8 mMole) of FeC13 in 100 ml of THF are saturated with propene (1 bar) at 0C; immediately afterwards 4.87 g (0.70 Moles) of lithium sand are added to the solution in propene atmosphere at 0C and with mixing (molar ratio 3a:FeC13:Li = 1:2:143). After a temporary temperature .

.. 1144533 rise, the propene absorption starts after 10-15 minutes.
During the propene absorption,the suspension is stirred, the propene pressure is kept at 1.1-1.2 bar and the temperature is kept at 0C to+2C. Tlle reaction mixture absorbs until saturation within 71 hours, 3.8 liters of propene (1 bar,20C).
The suspension is filtered and the lithium hydride is washed with THF. Of the total of 114.0 ml of the filtrates, 8.0 ml are hydrolyzed as described in example 1 whereby 351 ml of gas ~1 bar, 20C) with the composition propene, 75.7%; THF, 7.8%; H2, 8.7~, and acetylene 2.i% are released. From the amount of propene, a total yield of LiC3H5 of 45% is calculated accordiny to Equ. 8. In the silylation of an aliquot of filtrate, as described in example 1, one obtains a mixture of isomeric silanes ~CH3)35iC3H5, of the following composition:
trans -1- propenyltrimethylsilane, 83.8%; cis-l-propenyltrimethyl-silane, 1.3%; isopropenyltrimethylsilane, 10.3%; and allyltri-methylsilane, 4.6%. This result means that in the present case the catalytic lithiation of propene occurs with a selectlvity of 83.8~ in the trans -l-position of the propene;

Examples 3 to 12 For the preparation o~ the 2,4-diphenyl-1,6,6a-trithiapentalene ~
2CuC12- complex (15) Example 6, 3.09 9 (23.0 mMoles) of anhydrous copper(II)chloride are suspended in 100 ml of toluene, added to

-31-~W~J 2 CuC1 . , .
_ 15 3.73 g ~12.0 n~oles) of 2,4-diphenyl-1,6,6a-trithiapentalene, and the mixture is stirred for 18 hours at room temperature.
The suspension is filtered, the precipitate is washed.with toluene, and dried at 10-3 torr. One obtains 4.0 g (60% of theoretical) of the complex (15). C17~12S3Cu2C14 (580.8).
calc. C 35.12, H 2.07, S 16.56, Cu 21.88, Cl 24.41. Found C 34.85, H 2.55, S 16.34, Cu 21.78, Cl 24.35.
~. ', . .

Implementation of the examples 3 to 12 (.Table 1): the components of the catalysts are previously added to THF, the suspension is stirred if appropriate for 12 hours at 20C; immediately thereafter, the preparations are saturated at respective reaction temperature with.propene (1 bar), and lithium sand is added in a propene atmosphere under stlrring. The amounts of propene absorbed after specific reaction times (in liters, at 1 bar, 20C), as well as the yields of LiC3H5 and the isomer ratios (9:10:11:12) are indicated in Table 1. The determination of the yields and the isomer ratios are carried out as described in Example 1.

.

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_ _ _ _ _ _ 114~533 Examples 13 to 24 Implementation of Examples 13 to 24 (Table 2):

4,5-Benzo-1,2-dithiol-3-thione (BDT) (3a) and respective metal salt (molar ratio BDT:metal salt = 1:2) are stirred in 60 ml of THF for 12 hours at 20C; immediately afterwards, the prepara-tion is saturated at 0C with propene (1 bar), and lithium sand is added in a propene atmosphere and under stirring. The amounts of propene absorbed after specific reactiontimes (in liters, at 1 bar, 20C), as well as the yields of LiC3H5 and the isomer ratios (_:10:11:12) are indicated in Table 2. The determination_ _ of the yields and the isomer ratios are carried out as described in Example 1.

Examples 25 to 27 Preparation of the ortho-chloropalladio-2,5-diphenyl-1,6,6a-trithiapentalene complex (8) (Example 25):

To the suspension of 3.10 g (9.94 mMole) of 2,5-diphenyl-1,6,6a-trithiapentalene in a mixture of 230 ml of methanol and 25 ml of benzene, one adds 1.76 g ~9.92 mMoles) of PdC12 followed by 1.33 g (31.3 mMoles) of LiCl dissolved in 20 ml methanol.
The suspension is boiled for 3 hours under stirring, with reflux, and after cooling to room temperature it is filtered through a G-3 glass filter crucible. In the mother liquor, 93.6% of the split-off HCl was determined acidimetrically. The precipitate was washed with methanol and ether and was dried at 10 torr. The yield of (8) (M.P. 304C, decomp.) amounts to 4.38 g (97~).
C17Hl1S3PdCl (453.8);
Calc. C 44.94, H 2.64, S 21.15, Pd 23.44, Cl 7.82;
Fd. C 44.92, H 2.90, S 21.08, Pd 23.21, Cl 7.86.

Implementation of Examples 25 to 27 (Table 3):

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The solution or suspension of the catalyst in THF is saturated at 0C with propene (1 bar) and immediately thereafter lithium sand is added in a propene atmosphere and under stirring. The amounts of propene absorbed at the specific times (in liters, at 1 bar, 20C), as well as the yields of LiC3H5 and the isomer ratios (9:10:11:12) are indicated in Table 3. The determina-tion of the yields and of the isomer ratios was carried out as described in Example 1.

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Examples 28 to 33 L ~ s 2 FeCl~

(16) preparation of 4,5-benzo-1,2-dithiol-3-thione 2 FeC13- complex (16) (Example 29):

To the suspension of 1.89 g (11.6 mMoles) of the anhydrous FeC13 in 80 ml of benzene, the solution of 1.07 g (5.8 mMoles) of 4,5-benzo-1,2-dithiol-3-thione (3a) in 70 ml of benzene is added in dropwise fashion with stirring; immediately thereafter, the mixture is stirred for 24 hours at 20C. The suspension is filtered, the precipitate is washed with benzene and dried at 10 3 torr. One obtains 2.36 g (80% of theoretical) of the complex (16). C7H4S3Fe2C16 (508.7);
calc. C 16.52, H 0.78, Fe 21.97, S 18.90, Cl 41.84;
fd. C 16.55, H 0.82, Fe 21.91, S 18.84, Cl 41.76.

Implementation of Examples 28 to 33 (Table 4):

The catalysts are previously added to THF, the solution is saturated with ethylene (1 bar) at 0C; immediately thereafter, lithium sand is added at 0C under stirring, in an ethylene atmosphere. The amounts of ethylene absorbed after specific reaction times (in liters, 1 bar and 20C) are indicated in Table 4. The suspensions were filtered and the lithium hydride was washed with THF. In order to determine the yield of vinyllithium ~7 ~4533 in the filtrate, aliquots of the filtrate were concentrated under vacuum and the residues were hydrolyzed. From the amounts of ethylene developed and on the basis of Equ. 7, the yields of vinyllithium indicated in Table 4 were calculated.

In order to isolate the vinyllithium, in Example 28, 85 ml of a total of 90 ml of the filtrate were concentrated under vacuum (0.2 torr), the residue was stirred with 50 ml of pentane for 30 minutes, the suspension was filtered and the solid was washed four times with 10 ml of pentane each. Upon cooling the filtrate to -40 C, the vinyllithium-tetrahydrofuran adduct crystalize~
(2.72 g) in the form of colorless crystals.
C6H11OLi (106.1);
calc. 6.60 % Li;
fd. 6.60% Li.

In order to determine the lithium hydride, in Example 32, the lithium hydride obtained upon filtration was dried at 0.2 torr, yielding 4.1 g of a gray powder with 46.7% Li. Of this powder, 0.158 g yielded upon hydrolysis the following: HD 75.0%;
D2 6.3%; H2 6.3%; C2H3D 2.1%; and THF 1.3~. From the amount of HD, a yield of LiH of 69~ was calculated according to Equ. 7.

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~44S33 Example 34 ln 100 ml of absolute THF, the following are consecutively dissolved: 0.78 g (4.2 mMoles) of 4,5-benzo-1,2-dithiol-3-thione (3a); 1.38 g (8.5 ml~oles) of anhydrous FeC13; and, at 0C, 24.2 g (0.43 Moles) of 1 butene; immediately thereafter, the solution was mixed at 0C and under stirring, with 7.30 g (1.05 l~ole) of lithium sand. The reaction mixture was stirred a total of 7 days at 0C. During this period, 5.0-ml samples of the solution were withdrawn, filtered, and their lithium content was determined acidimetrically. After 17 and 70 hours of reaction time, the samples were found to contain 6.75 and 10.6 g-atoms of lithium, corre;sponding to a lithium conversion to lithiumbutenyl and 3ithium hydride,according to Equ. 9, of 26 and 40%. After 7 days of reaction time, the reaction mixture was separated by filtration from the lithium hYdrideand the un-converted lithium, and the precipitate was washed with THF. A
4!5-ml sample of the filtrate (of a total of 138 ml) yielded upon hydrolysis 218 ml of gas (at 20C, l bar), with 62.5~ vol.
of butene-l. From this, a yield of LiC4~17 of 40~ was calculated according to Equ. 9 In order to characterize the lithium butenyl, the remaining amount was mixed with an excess of trimethylchlorosilane in ether, as described in Example l. This yields 26.2 g of a mixture of the _ _ four isomeric compounds (CH3)3SiC4H7 (B.P. 95-109 C/760 torr), of which the main component is represented at 87.9%, according to the gas chromatogram. According to the lH-NMR-spectrum, H(~ (100 Mhz, 15 ~ in C6H6, ~ =
(~)(H3C)3Si ,~(~) / CH3 (~) 3.89 m (H(~;)), 4.34d (H(~)), \~' CH2 7.98 m (H(~)), 9.08t (~)) and H (~ 9.91 s (H~)); I12 = 18.5 Hz) (17) the major component is trans-l-trimethylsilyl-l-butené (17), which means that the lithiation occurs with a selectivity of 87.9%
in the l-trans position of l-butene.

Example 35 In a manner analogous to that of Example 34, 41.4 g (0.74 Mole) of l-butene are allowed to react in the presence of 2.15 g (4.75 mMoles) of complex (13) (Example 1) as catalyst, with 5.60 g (0.81 Mole) of lithium sand in 150 ml of THF for 10 days at 0 C.
The mixture is f.ltered and the solid (LiH + Li) is washed with THF. Of the filtrate (totalling 186 ml), 5.0 ml yield, after evaporation of the THF and subsequent hydrolysis, 191 ml of gas (at 20C, 1 bar), with 80% l-butene (balance: THF, H2 and C2~2).
On that basis, and following Equ. 9, one calculates a yield of LiC4H7 of 58% (referred to Li). In order to isolate the trans-l-lithio-l-butene, 110 ml of THF is distilled off from the remaining filtrate under vacuum (0.2 torr), 100 ml of pentane are added, -` 1144533 and the mixture is filtered ~free of~ catalyst remnants at O C.
Upon letting the filtrate stand at -78C overnight, further remnants of the catalyst are separated. The supernatant solution is fully evaporated under vacuum (0.2 torr), the residue is dried for several hours at 10 3 torr, taken up in 120 ml of pentane, stirred for a short time and filtered. The white frit residue is washed with pentane and dried under 0.2 torr. One obtains 7.8 g of trans-l-lithium-l-butene, containing 9.48% Li.
After the silylation of this product with trimethylchlorosilane, processing and distillation, as descirbed in Example 1, this yields trans-l-trimethylsilyl-l-butene at 97% taccording to GC analysis), which was identified by lH-NMR-spectroscopy.

Example 36 In a suspension of 0.58 g (1.28 mMoles) of 8 (see Examples 25 to 27) in 20 ml of THF, 1.81 liters (76 mMoles) of gaseous l-butene are dissolved, which is followed by mixing the suspension at 0 C under stirring with 0.92 g (0.13 Mole) of lithium sand. After stirring for 50 hours at 0C it is filtered and the lithium hydride is washed with THF. An aliquot of the solution (4.0 ml of a total of 43.6 ml) yields after evaporation of the THF and hydrolysis, 200 ml of gas (at 20C, 1 bar) with a total of 30.0% butenes. On the basis of the amount of butene one calculates a yield of ~iC4H7 of 40.7%. Upon mixing an aliquot of the solution with trimethyl-chlorosilane, as described in Example 1, one obtains a mixture of ~.

`` 11~4533 the isomeric silanes (H3C)3SiC4~37, which are, according to the lH-~r~R-spectrum or GC analysis, predominantly a mixture of cis-and trans-l-trimethylsilyl-2-butene.

E~ample 37 Tl~ a suspension of 6..29 g (0.91 Mole)of lithium sand in 100 ml of TH~ are added at 0C and under stirring, in consecutive order,

33.8 g (0.48 t~ole) of l-pentene and 1.45 g (2.85 mMole) of complex 16 (Examples 28 to 33). The mixture is stirred for 5 days at 0C, followed by filtration and washing of the solid (LiH) with THF.
Of the total of 169 ml of filtrate, 2.50 ml contain, according to the aciaimetric lithium determination, 4.30 g-atoms of Li, which corresponds to a yield in LiC5Hg of 64%.

In order to chara~terize the ~rganolithium compound LiC5Hg, 86.5 ml of the filtrate are mixed with excess trimethylchlorosilane, as described in Example 1. Procéssing or distillation yields, among others, 10.6 9 of a fraction (B.P. 133C/760 torr), which is trans-l-trimethylsilyl-l-pentene (18), according to the l~-Nt~R-spectrum.

(80 tlH2, 15 ~ in CDC13; ~ 3 =.96 m (H1~, 4.39 d (l~, 7.90 m 0 (l13~, 8.57 m (H~), 9.09 t 3 )3 ~ Cl ~ l2 ~ Cl~ 18 5 l~z) (lB) In order to isolate the trans-l-lithio-l-pentene, 80 ml of the ~1~4S33 filtrate are concentrated under vacuum to 20 ml, are mixed with 80 ml of pentane and filtered. The filtrate is kept for 12 hours at -78C, and is then syphoned off at -78C from the catalyst remnants that separated. The solution so obtained is completely evaporated under vacuum, the residue is dried at 20C and 10-3 torr to constant weight, is taken up in 100 ml pentane, stirred for one-half hour and filtered. The white precipitate is washed with pentane and dried at 0.2 torr. One obtains 3.14 g of trans-l-lithio-l-pentene in the form of white powder. LiC5Hg (MW = 75.9);calc. 9.32 ~ Li; fd. 9.29% Li.

.
Example 38 In a manner analogous to Example 34, 21.6 g (0.20 Mole) of 1,7-octadie~e are left to react in the presence of 1.25 g (2 76 mMoles) of complex 13 (Example 1) as catalyst, with 5.~2 g (0.84 Mole) of lithium sand in 150 ml of THF for 11 days at 0C. The suspension is filtered and lithium hydride is washed with THF.
Of a total of 17 ml of the filtrate, 5.0 ml contain, according to the acidimetric determination, 6.94 g-atoms of lithium, corresponding to a total yield of organolithium compounds of 57%.

The orqanolithium compounds in solution are characterized in the form of their trimethysilyl derivatives. For that purpose, 77 ml (of a total of 172 ml) of the solution, are mixed with trimethyl-chlorosilane as described in Example 1. The processing or distillation yields 7.67 g of a fraction with B.P. 55-63 C/0.7 torr, as well as 1.55 g of a fraction of B.P.54-55 C/10 torr.
According to the H-NMR-spectrum, the first fraction consists of trans-l-trimethylsilyl-1,7-octadiene (19), and the second fraction essentially of bis-1,8-(trans-trimethylsilyl)-1,7-octadiene (20), i.e., (CH3)3Si ~ (C 2)4CH CH2(CH3)3Si ~ CH2CH2-H H . 2 (19) _ in the case of 1,7-octadiene, the lithiation also occurs with high selectivity in the trans-l position.

Example 39 In 150 ml of absolute THF there are suspended or dissolved con-secutively 1.79 g (3.95 mMoles) of complex 13 (Example 1), as well as 13.0 g (0.19 Moles) of 1,4-pentadiene; immediately thereafter one adds to the suspension, at 0C under stirring, 11.1 g (1.60 Mole) of lithium sand. The reaction mixture is stirred for 74 hours at 0C. After this time period, a 5.0-ml sample of the solution contains 9.42 mg atoms of lithium. The suspension is diluted with 50 ml of THF, filtered at 0 C and the LiH is washed with THF. During the 48-hour standing of the solution at -78C, 11~4533 the organolithium compound 14 crystalizes out in the form of brown-color, coarse crystal. The crystals are separated from the mother liquor at -78C, are washed with a little T~F cooled to -78C and dried for one-half hour at 0C and one-half hour at 20C under vacuum (0.2 torr). One obtains 11.1 g of product with a ratio of 9.61% lithium (calc. for C4H5Li3(THF)2 9 0~ Li).
On the basis of the H-NMR or C-NMR-spectra in combination with spin-spin-decoupling experiments, as well as on the basis of the silylation (see below), the organolithium compound is assigned structure 14. In oxder to record the H-NMR-spectrum, the product, with 9.61 % Li, is recrystalized twice from an 1:1 THF-tetramethyl-ethylenediamine mixture (crystalization respectively at -78C).
The H-NMR-spectrum of 14 (15% in d8-THF; 270 MHz; 27 Ci d-THF
as internal standard ): ~ = 7.54 dd (Hl), 5.37 d(H3), 4.79 d (H4), 3.03 d (H5), 2.95 d (H ), 3.54 m and 1.68 m (THF), 2.21 s and 2.06 s (tetramethylenediamine); I12 - 16.3 Hz, I13 = 5.4 Hz, I45 = 4.2 Hz.

~ Li ¦ ~

In order to record the 3C-NMR-spectrum, the raw product is recrystalized from THF (crystalization at -78 C). The C-N~R-- ,j spectrum of 14 (100 MHz; 10% in d8-THF, at 25 C); ~ (ppm)=
84.6 t (C5), 97.6 (wide) (Cl), 100.4 d (C3), 153.9 d (C2), 187.7 (wide) (C4). The widening of the signals of the Cl and 13C4 nuclei indicates the presence of two Li-C bonds. In the reaction of 1.07 g of 14 with trimethylchlorosilane, as described in Example 1, one obtains, after processing or dis-tillation, 0.85 g of a fraction of B.P. 45-47 C/10 torr, which, according to the H-NMR-spectrum, is a mixture of the three stereoisomeric 1,4,5-tris (trimethylsilyl)-1,3-pentadienes (21) (65%), (22) (33~), and (23) (2%).

SiMe3 SiMe3 Me351 ~ ~e35i Si~e3 SiMe3 SiMe3 Me3Si ~

SiMe3 ~n It was shown in a parallel experiment that in the reaction of pentadiene-1,4 with lithium, under the same conditions of reaction but in the absence of the catalyst, the formation of 14 occurs at best in trace quantities only.

Example 40 S_ S _S
H5C6 ~ C6H5 A solution of 0.34 g (1.1 mMoles) of 2,5-diphenyl-1~6,6a-trithia-pentalene 24 and 0.30 g (2.2 mMoles) of NzC12 (anhydrous) in 50 ml of absolute THF, is saturated at 0C with ethylene (1 bar);
immediately thereafter the preparation is mixed in an ethylene atmosphere at 0C and under stirring, with 1.45 g (0.21 Moles) of lithium sand. After a slight rise in temperature, ethylene absorption starts after 10-15 minutes, the rate of absorption being measured with the aid of a gas burette attached to the reaction vessel.
During the ethylene absorption, the suspension is vigorously stirred and the temperature is kept at 0C. Up to the end of the reaction, the reaction mixture absorbs within 6 hours 2.28 liters of ethylene (1 bar, 20C). The suspension is filtered to separate the lithium hydride, and the lithium hydride is washed with THF.
Of the total of 81.0 ml of the filtrate, 50 ml yield after evaporation ~7 - ` 114~533 of the THF, upon hydrolysis, 126 ml of gas (at 20C, 1 bar), which, according to MS analysis consists of 84.8 Mole% of ethylene. On the basis of the amount of ethylene obtained during hydrolysis, the vinyllithium yield is calculated according to Equ. 7 at 76% (referred to ethylene).

Example 41 A solution of 1.61 g (5.2 mMoles) of 2,5-diphenyl-1,6,6a-tri-thizpentalene (24) and 1.21 g (8.9 mMoles) of ZnC12 (anhydrous) in 100 ml of absolute THF is saturated at 0C with propene tl bar);
immediately thereafter the preparation is mixed in a propene atmosphere at 0C and under stirring with 5.47 g (0.79 Moles) of lithium sand. The further pe~rformance of the experiment followed Example 40 as described for ethylene. Up to the end of the reaction, the reaction mixture absorbed within 12 hours 7.9 liters of propene (at 20C, 1 bar). The suspension was filtered and the lithiumhydride washed with THF. Of the total of 167.0 ml of filtrate, 7.0 ml yielded upon hydrolysis 372 ml of gas (20~C, 1 bar), consisting of 88.8 Mole~ of propene(balance: THF, H2).
From the amount of propene obtained upon hvdrolysis, the yield of organolithium compounds LiC3H5 was calculated according to Equ. 8 at 99.7% (referred to propene). The mixing of 40 ml of the filtrate with trimethylchlorosilane,and thesubsequent processing and distillation, as described in Example 1, yielded 11.9 g of the isomeric silanes (CH3)35iC3l~5, with the composition: trans-l-pro-penyltrimethylsilane, 80.0%; cis-l-propenyl-trimethylsilane, 0.4~;

S3;~

isopropenyltrimethylsilane, 15.0%; and allyltrimethylsilane, 4.6%. The isolation of the organolithium compounds LiC3H5 from the THF solution, as described in Example l, yields a product that consists of 91.3% trans-propenyllithium.

.
EY.ample 42 To a solution of 25.1 g (0.22 Mole)of l-octene and 1.23 g (4.0 mMoles) of 2,5-diphenyl-1,6,6a-trithiapentalene (24)in 100 ml of absolute THF, there are added consecutively at 0C and under stirring,1.15 g (8.5 mMoles) of ZnC12 (anhydrous) and, in small portions, 3.09 g (0.45 Moles) of lithium sand. The preparation was stirred for a total of 22 hours at 0C. During this period, 2.5-ml samples were withdrawn from the solution, filtered, and the lithium content in the filtrates determined acidimetrically. After 3.5, 6, and 22 hours, the lithium content in the samples is 4.2, 4.6 and 5.4 mMoles, respectively, corresponding to a lithium conversion to lithium octenyl and lithiumhydride, according toFqu. 9, of 75, 83 and 97%.
The ?reparation is filtered and the lithiumhydride is washed with THF. Of the total of 167.0 ml of the filtrate, 47.0 ml are mixed, as described in Example 1, with 11.0 g (0.10 ~oles) of trimethyl-chlorosilane. The processing or distillation yields 6.13 g of a fraction of B.P. 35-43C/0.2 torr, which, according to GC analysis or GC-MS-coupling analysis and lH-NMR-spectrum, consists of 96.6%
of trans-l-trimethysilyl--l-octene (25). According to this result, -~6-11~4533 \ C ~ \ tCH ) CH

.

l-octéne is lithiated according to the method described with a selectivity greater than 96~ in the trans-l position.

.
Herein and in the claims, the catalyst is defined in the manner conventionally used in the art, i.e., in terms of its components, ra~her than attempting to speculate on the nature or structure of an active material which may be formed from these components.

This application is a division of Canadian Patent Application serial number 347,087, filed March 5, 1980.

.. . . _

Claims (28)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A catalyst comprising a composition of the formula wherein A and B are sulfur or oxygen;
G is a carbon atom bonded to a radical R1;
D is a carbon atom bonded to a radical R2 and there is a double bond between the carbon atom of G and D;
E is carbon;
F is oxygen, sulfur, , or ;
Me is an alkaline metal;
n is an integer from 2 to 20;
L and L' are mono or poly-functional ethers or amines;
p and q are integers from 0 to 4;
R1, R2, R3 and R4 are independently hydrogen, alkyl, cycloalkyl, aralkyl or aryl groups, and/or two or more of such groups are closed into an aliphatic or aromatic ring system; and a metal compound of transition metals from group Ib, IIb, IVb, Vb, VIb, VIIb, and VIII of the periodic system.

2. The catalyst according to claim 1, wherein the composition has the formula in which X is sulfur or oxygen.

3. The catalyst according to claim 2, wherein the composition has the formula

4. The catalyst according to claim 3, wherein the metal compound is cupreous chloride or ferric chloride.

5. The catalyst according to claim 1, wherein the composition has the formula II

in which X is sulfur or oxygen.

6. The catalyst according to claim 5, wherein X is sulfur, R1 = R4 is C6H5, R2 = R3 is hydrogen, and-Me is lithium.

7. The catalyst according to claim 6, wherein the metal compound is zinc chloride or palladium chloride.

8. The catalyst according to claim 5, wherein X is sulfur, R1 = R3 is C6H5, R2 = R4 is hydrogen, and Me is lithium.

9. The catalyst according to claim 8, wherein the metal compound is cupric chloride.

10. The catalyst according to claim 1, wherein the metal compound is of a metal selected from the group consisting of copper, gold, zinc, cadmium, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum.

11. The catalyst according to claim 1, wherein the metal compound is of a metal selected from the group consisting of copper, iron, zinc, palladium, platinum, and rhodium.

12. The catalyst according to claim 1, wherein the metal compound is selected from the group consisting of zinc chloride, iron (III) chloride, copper (I) chloride, copper (II) chloride, molybdenum (VI) chloride, titanium (IV) chloride, chromium (III) chloride, molybdenum (V) chloride, manganese (II) chloride, cobalt (II) chloride, nickel (II) chloride, nickel (II) acetyl-acetonate, rhodium (III) chloride, platinum (II) chloride, and palladium (II) chloride.

13. The catalyst according to claim 1, wherein the metal compound is an anhydrous metal compound.

14. A catalyst composition of metal complexes comprising a polycyclic aromatic compound, comprising a member of the group consisting of naphthalene, anthracene, phenanthrene, and diphenyl, an alkali metal, and a metal compound of tansition metals from group Ib, IIb, IVb, Vb, VIb, VIIb and VIII of the periodic system.

15. The catalyst composition according to claim 14, wherein the alkaline metal is lithium.

16. The catalyst composition according to claim 14, wherein the alkaline metal is sodium or potassium.

17. The catalyst according to claim 14, wherein the metal compound is a metalselected from the group consisting of zinc chloride, iron (III) chloride,copper(I) chloride, copper (II) chloride, molybdenum (VI) chloride, titanium (III) chloride, titanium (IV) chloride, chromium (III) chloride, molybdenum (V) chloride, manganese (II) chloride, cobalt (II) chloride, nickel (II) chloride, nickel (II) acetylacetonate, rhodium (III) chloride, platinum (II) chloride, and palladium (II) chloride.

18. A process for the preparation of a catalyst comprising contacting:
an organic compound of the formula wherein A and B are sulfur or oxygen, G is a carbon atom bonded to a radical R1, D is a carbon atom bonded to a radical R2 and there is a double bond between the carbon atom of G and D, E is carbon, F is oxygen, sulfur, or R1, R2, R3, and R4 are independently hydrogen, alkyl, cyclo-alkyl, aralkyl or aryl groups and/or two or more of such groups are closed into an aliphatic or aromatic ring system;
lithium; and mono- or poly-functional ethers or amines.

19, The process according to claim 18, further comprising adding to the resulting composition a metal compound of transition metals from group Ib, IIb, IVb, Vb, VIb, VIIb, and VIII of the periodic system.

20. The process according to claim 18, wherein the organic compound has the formula III

in which X is sulfur or oxygen.

21. The process according to claim 18, wherein the organic compound has the formula IV

22. The process according to claim 18, wherein the organic compound has the formula V

23. The process according to claim 22 wherein R1 = R4 is C6H5, and R2 = R3 is hydrogen.

24. The process according to claim 23, further comprising adding zinc chloride or palladium chloride to the resulting composition.

25. The process according to claim 22, wherein R1 = R3 is C6H5, and R2 = R4 is hydrogen.

26. The process according to claim 25, further comprising adding cupric chloride to the resulting composition.

27. The process according to claim 18 wherein the organic compound has the formula VI

28. The process according to claim 18, wherein the organic compound has the formula VII