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Some reactions of dialkyltin oxides with acetyl chloride and trimethylchlorosilane
Joumnl of Organometallic Chemistry, 99 (1975) C44-C46 0 Elsevier Sequoia Sk, Lausanne - Printed in The Netherlands
preliminary
communication
SOME REACTIONS OF DIALKYLTIN AND TRIMETHYLCHLOROSILANE
OXIDES WITH ACETYL CHLORIDE
SHIGEMI KOHAMA
llre Osaka Municipal
Technical
Research
Institute,
Kitaogimachi
38, Kita-ku,
Osaka (Japan) -
(Received August 8th, 1975)
Dialkyltin oxides react with acetyl chloride to give R2 SnClOAc or Rz SnClz , depending on the stoichiometry, and with Me3 Sic1 to give (ClR* Sn), 0.
It has been shown that dimethyltin dichloride reacts with acetic anhydride or glacial acetic acid to give dimethyltin chloride acetate [l] and that the reactions of various sym-(dichlorotetraalkyl)distannoxanes with acetic acid also give the corresponding chloride acetates [2]. Such chloride acetates now have been prepared by the reaction of dialkyltin oxide with an equimolar amount of acetyl chloride. Upon further addition of acetyl chloride, the dialkyltin chloride acetates were converted into the corresponding dichlorides. These also were easily formed from the oxides and a large excess of acetyl chloride. R2 SnO + AcCl
1
excess AcCl
It2 SnClOAc
1
R2 sJ1y
(R = CH3, Cz H5, n-C3 H, , n-C, Hg , n-C& H1, ) It was found that the rate of digestion of dialkyltin oxides in acetyl chloride followed the sequence CH3 < Cz H, < n-C, H, < n-C, H9 < n-C8 H1, for alkyl groups. Similar treatment of dialkyltin oxides with organic halides such as ethyl bromide, t-butyl chloride, ally1 chloride and benzyl chloride resulted in recovery of the starting materials. Unlike the case with acetyl chloride, the reaction of dialkyltin oxides
c ‘As dimer.
(3)
(3) R = n-O&
(3) R = n-O&
(3) R = n-Bu
(2) R = n.Bu
(2) R=mPr
(2) R=xvPr
(2) R = Et
(4) R = Et
(4) R=Me
R=Me
AcCl 1.9 Me,SiCI 2,6 AcCl 0.8 Me, Sic1 1.1 AcCi 0.1 Mu, SIC1 1.0 AcCl 1,O Me, &Cl 1.3 AcCl 0.1 Me, Sic1 0.9
Halide (9)
R, SnO
(B)
Reactants
(ClOct, Sn), 0
Ott, SnCl(OAc)
(CIBu, Sn), 0
Bu,SnCl(OAc)
(CIPr, Sn), 0
Pr, SnCl(OAc)
(ClEt, Sn), 0
Et,SnCI(OAc)
(CIMe, Sn), 0
Yleld
76 88.89
(61) 121 112-113 (111.112) [&I
(34!
:G, 2,7
(85)
(84) 288
(89) 3,3
(82) 2,o
(73) I21 121-122 (122) [41 65.66
(79) 2,2
(80) 18
(71) 2,2
(78) 3.3
4,6
(6(W)
(94) 121 174 (176.6) [41 74-7 6
(-) c31 93.04
189-190 (189) VI 200
Ma (“C) Found (Lit.)
OXIDES AND HALIDES
Me, SnCl(OAc)
Product
REACTIONS BETWEEN DIALKYLTIN
TABLE 1
48.81 (48.79) 61.74 (61.75) 43.74 (43,7G) G3.68 (63.88) 39.72 (39.66) 47.82 (47.79) 36.48 (36.26) 42.90 (42096) 26897 (26,99) 30.61 (30,64)
Sn
48,96 (48,18) 49,27 (49,46)
36,39 (36,66)
31,92 (32,09)
C
3.60 (8.48) P.90 (8.82)
0,64 (6.49)
5.76 (6.72)
H
Analysis (%) Found (calcd.)
8003 (8,06) 8,66 (9,12)
10.84 (10.83)
Cl
443 (439) 1600 a (777)
361 (327)
(299)
316
Mol.wt. Found (calcd.)
C46
with an equimolar
quanti4$ of trimethylchlorosilane
did not give the expected
trimethylsilyldialkylstannoxanes. Instead, sym-(dichlorotetraalkyl)distannoxanes were formed. The resulting distannoxanes were converted to dialkyltin dichlorides by further addition of trimethylcblorosilane. A large excess of trimethylchlorosilane, of course, converted the dialkyltin oxides directly to the dialkyltm dichlorides.
excess Me, Sic1
:
R2 SnClz + Me, SiOSiMe,
(R = CH3, Cz H5, n-C, H, , n-C, H, , n-C, Hi,) It was confirmed that in the early stages of this reaction the dialkyltin dichlorides existed in a liquid layer of the reaction mixture. A possible explanation of the formation of the distannoxane is the reaction between initially produced dichloride and the unreacted oxide. Evidence for this was provided by our fiiding that equimolar quantities of dialkyltin dichloride and dialkyltin oxide react quantitatively to yield the distannoxane. Thus the reaction steps for the formation of sym-(dichlorotetraalkyl)distannoxane are: R2 SnO + 2 Me3 Sic1 R2 SnCl, + R2 SnO
R2 SnCl, + Me3 SiOSiMe, * CIRl SnOSnR, Cl
Typical examples are shown in Table 1 (the octyl derivatives are new compounds) Acetyl chloride and dialkyltin oxides reacted exothermally when they were mixed in chloroform. On the other hand, since trimethylchlorosilane and the oxides did not react smoothly under the same conditions, they were heated at reflux until the oxide dissolved. The solvent then was removed under reduced pressure and the dialkyltin chloride acetates or sym-(dichlorotetraalkyl)distannoxanes were recrystallized from petroleum ether. They were characterized by m.p., analysis and, in some cases, by molecular weight deter-
mination. References 1 2 3 4 5
R. Okawara and E.G. Rochow. J. Amer. Chem. Sot.. 82 (1960) 3285. M. Wada, M. Shindo and R. Okawam. J. Organometi. Chem.. 1<1963) 95. R. Okawara. Proc. Chem. SOL. (1961) 383. RX_ In&ham. Chem_ Rev.. 60 (1960) 459. A.J. Gibbons, A.K. Sawyer and A. Ross. J. Or& Chem.. 26 (1961) 2304.
preliminary
communication
SOME REACTIONS OF DIALKYLTIN AND TRIMETHYLCHLOROSILANE
OXIDES WITH ACETYL CHLORIDE
SHIGEMI KOHAMA
llre Osaka Municipal
Technical
Research
Institute,
Kitaogimachi
38, Kita-ku,
Osaka (Japan) -
(Received August 8th, 1975)
Dialkyltin oxides react with acetyl chloride to give R2 SnClOAc or Rz SnClz , depending on the stoichiometry, and with Me3 Sic1 to give (ClR* Sn), 0.
It has been shown that dimethyltin dichloride reacts with acetic anhydride or glacial acetic acid to give dimethyltin chloride acetate [l] and that the reactions of various sym-(dichlorotetraalkyl)distannoxanes with acetic acid also give the corresponding chloride acetates [2]. Such chloride acetates now have been prepared by the reaction of dialkyltin oxide with an equimolar amount of acetyl chloride. Upon further addition of acetyl chloride, the dialkyltin chloride acetates were converted into the corresponding dichlorides. These also were easily formed from the oxides and a large excess of acetyl chloride. R2 SnO + AcCl
1
excess AcCl
It2 SnClOAc
1
R2 sJ1y
(R = CH3, Cz H5, n-C3 H, , n-C, Hg , n-C& H1, ) It was found that the rate of digestion of dialkyltin oxides in acetyl chloride followed the sequence CH3 < Cz H, < n-C, H, < n-C, H9 < n-C8 H1, for alkyl groups. Similar treatment of dialkyltin oxides with organic halides such as ethyl bromide, t-butyl chloride, ally1 chloride and benzyl chloride resulted in recovery of the starting materials. Unlike the case with acetyl chloride, the reaction of dialkyltin oxides
c ‘As dimer.
(3)
(3) R = n-O&
(3) R = n-O&
(3) R = n-Bu
(2) R = n.Bu
(2) R=mPr
(2) R=xvPr
(2) R = Et
(4) R = Et
(4) R=Me
R=Me
AcCl 1.9 Me,SiCI 2,6 AcCl 0.8 Me, Sic1 1.1 AcCi 0.1 Mu, SIC1 1.0 AcCl 1,O Me, &Cl 1.3 AcCl 0.1 Me, Sic1 0.9
Halide (9)
R, SnO
(B)
Reactants
(ClOct, Sn), 0
Ott, SnCl(OAc)
(CIBu, Sn), 0
Bu,SnCl(OAc)
(CIPr, Sn), 0
Pr, SnCl(OAc)
(ClEt, Sn), 0
Et,SnCI(OAc)
(CIMe, Sn), 0
Yleld
76 88.89
(61) 121 112-113 (111.112) [&I
(34!
:G, 2,7
(85)
(84) 288
(89) 3,3
(82) 2,o
(73) I21 121-122 (122) [41 65.66
(79) 2,2
(80) 18
(71) 2,2
(78) 3.3
4,6
(6(W)
(94) 121 174 (176.6) [41 74-7 6
(-) c31 93.04
189-190 (189) VI 200
Ma (“C) Found (Lit.)
OXIDES AND HALIDES
Me, SnCl(OAc)
Product
REACTIONS BETWEEN DIALKYLTIN
TABLE 1
48.81 (48.79) 61.74 (61.75) 43.74 (43,7G) G3.68 (63.88) 39.72 (39.66) 47.82 (47.79) 36.48 (36.26) 42.90 (42096) 26897 (26,99) 30.61 (30,64)
Sn
48,96 (48,18) 49,27 (49,46)
36,39 (36,66)
31,92 (32,09)
C
3.60 (8.48) P.90 (8.82)
0,64 (6.49)
5.76 (6.72)
H
Analysis (%) Found (calcd.)
8003 (8,06) 8,66 (9,12)
10.84 (10.83)
Cl
443 (439) 1600 a (777)
361 (327)
(299)
316
Mol.wt. Found (calcd.)
C46
with an equimolar
quanti4$ of trimethylchlorosilane
did not give the expected
trimethylsilyldialkylstannoxanes. Instead, sym-(dichlorotetraalkyl)distannoxanes were formed. The resulting distannoxanes were converted to dialkyltin dichlorides by further addition of trimethylcblorosilane. A large excess of trimethylchlorosilane, of course, converted the dialkyltin oxides directly to the dialkyltm dichlorides.
excess Me, Sic1
:
R2 SnClz + Me, SiOSiMe,
(R = CH3, Cz H5, n-C, H, , n-C, H, , n-C, Hi,) It was confirmed that in the early stages of this reaction the dialkyltin dichlorides existed in a liquid layer of the reaction mixture. A possible explanation of the formation of the distannoxane is the reaction between initially produced dichloride and the unreacted oxide. Evidence for this was provided by our fiiding that equimolar quantities of dialkyltin dichloride and dialkyltin oxide react quantitatively to yield the distannoxane. Thus the reaction steps for the formation of sym-(dichlorotetraalkyl)distannoxane are: R2 SnO + 2 Me3 Sic1 R2 SnCl, + R2 SnO
R2 SnCl, + Me3 SiOSiMe, * CIRl SnOSnR, Cl
Typical examples are shown in Table 1 (the octyl derivatives are new compounds) Acetyl chloride and dialkyltin oxides reacted exothermally when they were mixed in chloroform. On the other hand, since trimethylchlorosilane and the oxides did not react smoothly under the same conditions, they were heated at reflux until the oxide dissolved. The solvent then was removed under reduced pressure and the dialkyltin chloride acetates or sym-(dichlorotetraalkyl)distannoxanes were recrystallized from petroleum ether. They were characterized by m.p., analysis and, in some cases, by molecular weight deter-
mination. References 1 2 3 4 5
R. Okawara and E.G. Rochow. J. Amer. Chem. Sot.. 82 (1960) 3285. M. Wada, M. Shindo and R. Okawam. J. Organometi. Chem.. 1<1963) 95. R. Okawara. Proc. Chem. SOL. (1961) 383. RX_ In&ham. Chem_ Rev.. 60 (1960) 459. A.J. Gibbons, A.K. Sawyer and A. Ross. J. Or& Chem.. 26 (1961) 2304.