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Preparation of dialkyltin dinitrates
291
SHORT CO~DIbXIC_~TIOSS
Melting points were obtained both from a Fisher-Johns instrument and on a DuPont goo DifEerentialThermal _%nalyzer. Infrared spectra were recorded as Xujol mulls on a Baird infrared recording spectrophotometer Xodel 4-55 ar;d on a Per&r-Elmer 337 grating infrared spectrophotometer, calibrated with Polyst>Tene film. Elemental analyses were carried out by Dr. C-ROL Ii- FITZ, Needham Heights, Massachusetts and Galbraith Laboratories, Inc., Knoxville, Tennessee. Easfzrtr Waylatrd,
Research
Laborafory,
3lassaclrusett.s
The Do-;r Cknaical
(U.S.A.)
Conapany,
H-G.
LAXGER BLUT
A. H.
I F. A. Corms _=D R- FR_~~cIS, J_ Am. Chcm. Sac., Sz (1960) -_g561 S. A. XSI-WNOFF _GD R. S. DRIGO. Ixor,o. Chem.. 3 (x96+) 337_ 3 K. Hrr~s ASD 31.C. HESRY. J_ Orpnonretal. Chenx.. 3 (1963) 139. + F. A_ Conox. R. FRASCIS ASD \V. D. HORROCK~, JR..J.Phys. Chcm..63 (1960) 153+ =j_X.L. _hLED _=D E. G. Roaio\\-, J. Inoq. A-ud. Claem., 5 (195s)269. 6 D. COOK, Calr. J_ Chcnz.. +I (1963) 51-z. ; H. GIL~AS, OIJUH~GChe~:is:ry.V~l. 1, \\Xley, Sew York. 2nd ed.,x9.+3. S S. A. 1\Lav.--luom ASD R. S. DX_IGO.J- Or~anontetol. Chem.. 3 (1965) 393.
Received June 25th. 1965 J_ Or~anonzeiat. Chum., 3 (1966) 4S-zgI
Preparation
of dialkyltin
dinitrates
Trialkyltin nitrates’ have been prepared by the interaction of the appropriate trialkyltin halide with alcoholic silver nitrate solution. The preparation of dimethyltin dinitrate from tetramethyltin and liquid dinitrogen tetroside”, and also from dimethyltin oside and nitric acid3 has recently been reported. The preparation of diethyltin din&ate’ is claimed in the early literature. 11-e now report the preparations of dimethyltin dir&rate and the previously unreported di-wpropyltin and di-+butyltin dinitrates by the silx-er nitrate method.
The x,ro-phenanthroiine compIeses of the di-jr-propyltin and di-jr.-but>-ltin&nitrates have been prepared. The dialkyitin dinitrates are x-cry deliquescent compounds which are soluble in polar org‘anic sol\-ents. The nitrates undergo decomposition xith the liberation of oxides of nitrogen at room temperature even when stored in a sealed tube, but they can be stored at low temperatlnre (---IS’) without appreciable decomposition. The I,Io-phenanthroline compieses, on the other hand, are perfectly stable at room temperature and are non-deliquescent. The SNR and IR spectra of these compounds are being studied.
Di-tt-jrop_vlfix di&mte’. Silver nitrate (36.90 g, 2.0 mol_) in a Soxhlet thimble was extracted for several hours bv k- methanol (ZOO ml) in which &-sr-propyltin dichloride (30-o g. 1.0 mol.) was dissolved. The precipitated silver chloride (31.4 g, - xoo 56) was remox-ed b>- filtration. Evaporation of the f&rate at ZO'/O.I mm, folJ_ Or,oaaomeial. Chem.. 5 (1966)zgr-zgz
SHORT COMMCSs‘IC_-iTIOSS
292
lowed by recrystallization from chloroform yielded di-wpropyltin &nitrate, m-p. x37-13s” (22.67 g, 634 o;;). (Found: Sn, 36-z C,H,,X,O& cakd.: Sn, 36.0 ~&) Dim&hyItir, dinitrate(IZOO g, gzo 3;). (Found: Sn. 43-S. C,H,S,O$n c&d. : w-z similarly obtained from &methyl& dichloride (ro.gr g, 1.0 mol.) and Sn. 43-5 %-) silver nitrate (1627 gt 2.0 moI.). IX+;-b@.$& dirzi~rafz’ (657 x), m-p. ro3.5--104.5”, (Found: Sn. 334 C,H,,S,O&n cakd.: Sn, 33.2 :A_) was aI% prepared b>- the same method_ Di-~-]~&Iti>r dijtitratt-l,m-plt~i~~~~r~!i~:e~_ r.Io-Phenanthroline hydrate (s.o g. 1-0 mol_) in absolute ethanol (25 ml) was added to d&z-prop+n din&-ate (3-3 g, x.0 moL) in the same solx-ent (35 mlj with shaking. The white precipitate. which formed immediately. was recrystaltised from absolute ethanol to yield the&n-prop+ tin din&rate x,Io-phenanthroline cornpIes (4.S g, 93.7 so), m-p_ zos-206” (de@. (Foxmd: C. 42.0; Z-I, q-4; S. 11-6; Sn 23_3_ C,,H,,S,O$n calcd.: C, qz.5; H. 1-3: s. lx.0; Sn. “-3.3 Yb_) Di-dmfylis dilrifrall-r,ro-~lrznalrilrroZi~le’ (5-2 g, 96.0 yO), m.p. zag-zra' (dec.), (Found: C. 11-5; H. 4-S; S. IO-I; Sn , z.o_ C,H,S,O& c&d.: C, g-7; H. 4-9: S. 104: Sn. 22-0 ?&_)was similad~ obtained from di-7r-but-kin dinitrate (3.6 g, x.0 moi.) and r.so-phenanthroline hydrate (2.0 g. 1-0 mol.)_
ExpUosion
hazard:
benzene-z-cyclopentdienyiiron
(II) perchlorate
We wish to report that benzene-_~~~ciopentadien~liron(IL) perchlorate, i_C,Ha(ri-C,H,~FeICIO,, is potent&&- very dangerou5 It crystaUize5 from akohotic solution as yellow-brown prisms. It detonated violent& when touched with a spatula after recrystallization. The worker involved severely injured one hand and lost his thumb. Two months after the accident he died from esten+e firer damage. The cawe of this damage is, as J-et, unkncwn but tosication from the origina esplosion has not been tied out.
SHORT CO~DIbXIC_~TIOSS
Melting points were obtained both from a Fisher-Johns instrument and on a DuPont goo DifEerentialThermal _%nalyzer. Infrared spectra were recorded as Xujol mulls on a Baird infrared recording spectrophotometer Xodel 4-55 ar;d on a Per&r-Elmer 337 grating infrared spectrophotometer, calibrated with Polyst>Tene film. Elemental analyses were carried out by Dr. C-ROL Ii- FITZ, Needham Heights, Massachusetts and Galbraith Laboratories, Inc., Knoxville, Tennessee. Easfzrtr Waylatrd,
Research
Laborafory,
3lassaclrusett.s
The Do-;r Cknaical
(U.S.A.)
Conapany,
H-G.
LAXGER BLUT
A. H.
I F. A. Corms _=D R- FR_~~cIS, J_ Am. Chcm. Sac., Sz (1960) -_g561 S. A. XSI-WNOFF _GD R. S. DRIGO. Ixor,o. Chem.. 3 (x96+) 337_ 3 K. Hrr~s ASD 31.C. HESRY. J_ Orpnonretal. Chenx.. 3 (1963) 139. + F. A_ Conox. R. FRASCIS ASD \V. D. HORROCK~, JR..J.Phys. Chcm..63 (1960) 153+ =j_X.L. _hLED _=D E. G. Roaio\\-, J. Inoq. A-ud. Claem., 5 (195s)269. 6 D. COOK, Calr. J_ Chcnz.. +I (1963) 51-z. ; H. GIL~AS, OIJUH~GChe~:is:ry.V~l. 1, \\Xley, Sew York. 2nd ed.,x9.+3. S S. A. 1\Lav.--luom ASD R. S. DX_IGO.J- Or~anontetol. Chem.. 3 (1965) 393.
Received June 25th. 1965 J_ Or~anonzeiat. Chum., 3 (1966) 4S-zgI
Preparation
of dialkyltin
dinitrates
Trialkyltin nitrates’ have been prepared by the interaction of the appropriate trialkyltin halide with alcoholic silver nitrate solution. The preparation of dimethyltin dinitrate from tetramethyltin and liquid dinitrogen tetroside”, and also from dimethyltin oside and nitric acid3 has recently been reported. The preparation of diethyltin din&ate’ is claimed in the early literature. 11-e now report the preparations of dimethyltin dir&rate and the previously unreported di-wpropyltin and di-+butyltin dinitrates by the silx-er nitrate method.
The x,ro-phenanthroiine compIeses of the di-jr-propyltin and di-jr.-but>-ltin&nitrates have been prepared. The dialkyitin dinitrates are x-cry deliquescent compounds which are soluble in polar org‘anic sol\-ents. The nitrates undergo decomposition xith the liberation of oxides of nitrogen at room temperature even when stored in a sealed tube, but they can be stored at low temperatlnre (---IS’) without appreciable decomposition. The I,Io-phenanthroline compieses, on the other hand, are perfectly stable at room temperature and are non-deliquescent. The SNR and IR spectra of these compounds are being studied.
Di-tt-jrop_vlfix di&mte’. Silver nitrate (36.90 g, 2.0 mol_) in a Soxhlet thimble was extracted for several hours bv k- methanol (ZOO ml) in which &-sr-propyltin dichloride (30-o g. 1.0 mol.) was dissolved. The precipitated silver chloride (31.4 g, - xoo 56) was remox-ed b>- filtration. Evaporation of the f&rate at ZO'/O.I mm, folJ_ Or,oaaomeial. Chem.. 5 (1966)zgr-zgz
SHORT COMMCSs‘IC_-iTIOSS
292
lowed by recrystallization from chloroform yielded di-wpropyltin &nitrate, m-p. x37-13s” (22.67 g, 634 o;;). (Found: Sn, 36-z C,H,,X,O& cakd.: Sn, 36.0 ~&) Dim&hyItir, dinitrate(IZOO g, gzo 3;). (Found: Sn. 43-S. C,H,S,O$n c&d. : w-z similarly obtained from &methyl& dichloride (ro.gr g, 1.0 mol.) and Sn. 43-5 %-) silver nitrate (1627 gt 2.0 moI.). IX+;-b@.$& dirzi~rafz’ (657 x), m-p. ro3.5--104.5”, (Found: Sn. 334 C,H,,S,O&n cakd.: Sn, 33.2 :A_) was aI% prepared b>- the same method_ Di-~-]~&Iti>r dijtitratt-l,m-plt~i~~~~r~!i~:e~_ r.Io-Phenanthroline hydrate (s.o g. 1-0 mol_) in absolute ethanol (25 ml) was added to d&z-prop+n din&-ate (3-3 g, x.0 moL) in the same solx-ent (35 mlj with shaking. The white precipitate. which formed immediately. was recrystaltised from absolute ethanol to yield the&n-prop+ tin din&rate x,Io-phenanthroline cornpIes (4.S g, 93.7 so), m-p_ zos-206” (de@. (Foxmd: C. 42.0; Z-I, q-4; S. 11-6; Sn 23_3_ C,,H,,S,O$n calcd.: C, qz.5; H. 1-3: s. lx.0; Sn. “-3.3 Yb_) Di-dmfylis dilrifrall-r,ro-~lrznalrilrroZi~le’ (5-2 g, 96.0 yO), m.p. zag-zra' (dec.), (Found: C. 11-5; H. 4-S; S. IO-I; Sn , z.o_ C,H,S,O& c&d.: C, g-7; H. 4-9: S. 104: Sn. 22-0 ?&_)was similad~ obtained from di-7r-but-kin dinitrate (3.6 g, x.0 moi.) and r.so-phenanthroline hydrate (2.0 g. 1-0 mol.)_
ExpUosion
hazard:
benzene-z-cyclopentdienyiiron
(II) perchlorate
We wish to report that benzene-_~~~ciopentadien~liron(IL) perchlorate, i_C,Ha(ri-C,H,~FeICIO,, is potent&&- very dangerou5 It crystaUize5 from akohotic solution as yellow-brown prisms. It detonated violent& when touched with a spatula after recrystallization. The worker involved severely injured one hand and lost his thumb. Two months after the accident he died from esten+e firer damage. The cawe of this damage is, as J-et, unkncwn but tosication from the origina esplosion has not been tied out.