Commun. 1972, 339: D. J . U'utkin and 7: A. Hoinor, I Chem. SOC. B1971. 2167: K. lhrito, H . Shimunoirchi, and Y So.sudu, Chem. Lett. lap. 1973,269.  S fro, Y. Fukazawu, and Y Irrnka, Tetrahedron Lett. 1972. 741. 745, H. Shimanmichi and Y. Sosudu, ibid. 1970, 2421 ; Acrd Crysldllogr. B 2Y, 81 (1973). [R] Chem. SOC (London), Spec. Publ. No. 18 (1965).  M. Doblrr and J . D . Dunitz, Helv. Chim. Acta 4X, 1429 (1965). [lo] M Trutwubrrg, J Amer Chem. SOC.K6. 4265 (1964). [ I I] R . E . Dacis and A. Tulinsky,J. Amer. Chem. SOC.X K , 4583 (1966). [I21 E. h q r l and H . D . Roth. Angew. Chem 76, 145 (1964): Angew. Chem. internat Edit. 3, 228 (1964). Of the various trihalogermanes, only HGeQ and HGeBr3 have been previously reported ; they tend to decompose according to eq. (1b)['J or to GeX,, GeX, and H,[,]. Triiodogermane, HGe13, has been merely conjectured as an intermediate in germylation reactions of olefins with Ge12/50% aqueous Since we succeeded in preparing pure, GeBr4-free HGeBr3 by dissolving GeBr21sl in anhydrous HBr, we have found also that HGe13 is formed in quantitative yield when anhydrous HI is condensed on pure GeI, [eq. ( 1 a)]: HGeX, (1) The pale yellowish solution is stable below -50 C but at room temperature decomposes gradually thus: HGell + HI + Gela + Hz (2) (a. 50% after 7 days); dismutation to H2Ge12 and Ge14 was not observable. When the solvent HI is removed, even at low temperature, only GeIz is left as solid residue [eq. ( 1 b)]; and other attempts to prepare it-by HGeCI3/HI, HGeC13/GeI4 or HGeCI3/HSiI3 as reactants-lead also to Ge12. However, HGe13 is formed smoothly when an excess of HI is condensed on GeBr2, but in a suspension of Ge12 in 57 YOaqueous HI we could not prove the formation of triiodogermane. Thus HGe13 can exist only in liquid HI. But in such solutions we could measure the Raman spectrum, and this showed, as required for a CSr.molecule, three polarized and three depolarized lines (Table 1). The frequencies are in the expected regions, which can be derived from correlations and calculations for comparable vibrations for the series HGeX3 (X =C1, Br['] or I) and HGeX3/GeX4. Table I . Fundamental vibrations ( c m - ' ) from the Raman spectrum of HGel,. Type - ~ v, vz V3 E v4 vs ~6 -~ 20hX (0.5, p) 203 (10. p) 93 (5. P) 260 (1.5. dp) 66 (6, d p ) 643 (0.6, dp) ~ vGeH v,Gell F.GcI, vd<Ge13 6,9,Gel, GHGel .- -- A-XOIO Graz. Stremayrgiisse 16 (Austria) This work was supported by the Fonds zur Forderung der wissenschaftlichen Forschung, Vienna 856 Nucleophilic Ether Fissions by l,l-Diphenylhexyllithium'*'] By Gert Kiibrich and Annegrir Baurnann"] Because of the role of ethereal solvents in reactions of organometallic compounds, fission of ethers by organometallic and in particular organolithium compounds is very important. According to earlier investigations it is normally initiated by deprotonation at the 2- or P-carbon atom of the ether"]; very recent have uncovered an interesting meshing of a-, 0-and, a',p-eliminations for thecase ofdiethyl ether/alkyllithium. We propose to collect together under the general expression "protophilic ether fission" all those fissions that have proton abstraction from the ether molecule in the first reaction step as their common characteristic [eq. (I)]: Protophilic ether fission: I I I I - C-C -0-R' HV -C-~*-R' I 1 + consecutibe reactions We now report "nucleophilic ether fission" as a further type of reaction. This is a nucleophilic replacement by the organolithium compound [eq. (2)], in which an RO group of the ether constitutes the leaving group, thus playing the same role as do halogen atoms in the coupling of alkyl halides. Nucleophilic ether ,fission: ~ [*] Doz. Dr. F. Hofler and Dip].-lng. E. Brandstitter lnstitut fur Anorganische Chemie der Technischen Hochschule [**I  M . D. Ciirirs and P. Wdbvr, Inorg. Chem. 1 J , 431 (1972).  H. Sirherr -Anwendungender Schwingungsspektroskopieinder anorganischen Chemie. Springer, Heidelberg 1966. Assignment V .~ . AI [ I ] E. Wiberg and E . Ainbrryrr. Hydrides of the Elements of Main Groups I---IV. Elsevier, London 1971  M . L. D e l w u u l l ~ J~., Phys. Chem. 56, 355 (1952).  I' F . Mironol-, L. N . Kalinino, t;. M . Bvrliner, and 77 K . Cur, Zh. Obshch. Khim. 40, 2597 (1970). By Friedrich Hofler and Ernst Brandstatred'] + HX & Received: July 30. 1973 [Z X96 IE] German version: Angew. Chem. KS, 870 (1973)  P. ?ilu:rro//r.s and C . M a i w o l , Bull Soc. Chim. Fr. 1967. 251 I . Triiodogerrnane[**] GeXl vGeH and GHGeI are slightly dependent on concentration, being S-Scmhigher for very dilute solutions In thereaction ofstoichiometric amounts of HI with GeBrz or a GeBr4/Ge12 mixture there are formed, besides HGe13, the trihalides HGeBr12 and HGeBrJ, which also cannot be isolated but can be recognized from their main frequencies in the Raman spectrum (220 vs,p and 239 cm- V S , ~ ) . If we let aside those reactions, formally similar but different in kind, in which complex formation at the oxygen atom by a Lewis acid is the first step, as with triphenylmethyl an[*] Prof. Dr. G Kobrich and Dip].-Chem. A. Baumann lnstitut fur Organische Chemie der Tcchnischen L'niversitiit 3 Hannover, Schneiderberg I B (Germany) This work was supported hy the Dcutsche Forschungsgemeinschaft and the Fonds der Chemischcn Industrie. [**I 2-butenyl structure. The preponderating product from the isomeric 4-phenoxy-2-butene in T H F is the unrearranged product, but in hexane (in presence of 1 mol of tetramethylethylenediamine) it is mainly the unrearranged, sterically ions in presence of triphenyl-borane or -aluminum[3a1and very probably with Grignard reagents'3b1,then nucleophilic ether fission has been observed only with o x i r a n e ~ [and ~~] o x e t a n e ~ l ~which ~ ] , contain strained rings, and moreover Table 1 . Conditions and products of the reaction of 1.1-diphenylhexyllithium (DPHLi) with ethers [6, 71 Ether Ether: DPHLi Reaction conditions [b] Products and relative yields [d] Oxtrane I:I At 0 C instantaneous in T H F Oxetanc Tctrahydrofurdn ( T H F ) !:I [a1 17 h at room temp. in T H P 120 h at room temp. and 22 h at 7 0 T DPH--CH2-CHr-OH (70"4) + DPH-H (307;) DI'H-CH? ( ' I ] ? - - C H > OH ( l O O " 4 ) DPH -CH ,-CH ,-CH ,-CH ,-OH (84 %) + DPH-H (16",,) Tetrahydropjran ( T H P ) [a1 96 h at room temp and 22 h at 70-C [conversion 16 ""1 DPH-H H ,C=CH-0-C,H,-n 2: I H,C=CH-0-C,H,-iso 2: 1 [a1 1:1 72 h at 10h at 72 h at IOh at 18h at 22 h at 1: 1 1 S h at room temp. In T H F I:l 48 h at room temp. in hexane [c] D P H - C H z C H , (95%) + DPH-H ( 5 % ) DPH-CH=CH, (920/,) + DPH-H (87,) DPH-CH3(90g;)+ DPH-H ( < l o % ) DPH-CH=CH-C,H, ( t r a n s 78%,, C I S 147,) +DPH-CH3(5%J+DPH-H(3%) DPH-CH ,-CHzCH-CH, (94 %) DPH-CH(CH,)-CHyCH, (673 DPH-CH,-CH=CH-CH, (9%) DPH-CH(CH,)-CH=CH, (91 %) D PH -CH -C H =C H -C H (100 "<!) DPH-CHI-CH=CH-CH (1OO<) a ) Cyclic ethers (16",,) b) Acyclic ethers O--C'H.3 H-0-CH ('t,H- C',, H s--C'H-C C',,H5--O-CH? 3 -CH=CH--C'H, room 70 C room 70 C room room temp and in T H P temp. and in T H P temp temp. i n (C,H,),O 3 h at room temp. in T H F 36 h at room temp. In hexane [c] [a] [b] [c] [d] + + , , The cthcr studied served as solvent. Thc DPHLi was completely consumed, unless stated otherwise. In presence of I equivalent of tetramethylethylenediaminc Rctcl-red to DPHLi; about S0-90;,; thereof was isolated. only occasionally with tetrahydrofuran (THF) (with R,SiLi'5"l or triphenylrnethyllithi~m[~~~). As organometallic reagent we used 1 ,I-diphenylhexyllithium (DPHLi)l"l, which smoothly splits not only cyclic ethers but also alkyl phenyl, allyl and vinyl ethers (Table I). In all these cases nucleophilic predominates over protophilic fission. as is made evident by the poor yields of 1,l-diphenylhexane (DPH-H) which is the protonation product of DPHLi. Product analyses permit the following generalizations : 1. With cyclic ethers the ease of reaction increases with decreasing ring size, corresponding to increasing ring strain. Tetrahydropyran is no longer attacked nucleophilically ; and its protophilic fission by DPHLi at 70'C also occurs only to a small extent, so that this compound is more suitable as solvent for reactions involving DPHLi than is the commoner but less resistant THF. 2. Whereas the alkyl group of alkyl phenyl ethers is transferred to DPHLi [eq. ( 3 ) ] , it is the unsaturated group of alkyl vinyl ethers that is given up [eq. (4)]. This "transpolin&" indicates an addition-L.Iiiiiination reaction as mechanism for the vinyl ether fissions; it is faster than the S~Z-likctransfer of alkyl groups. DPHLi + C,,H1--O-Alkyl DPHLI + C'H2=CH-O-Alkyl - DPH-AIkyI + + C~HT-OLI DPH-CH=CHZ + Alkyl-OLt (3) (4) 3. Allylic rearrangement can accompany fission of substituted allyl ethers: 3-phenoxy-I-butene affords only the thermodynamically favored, rearranged product with the disfavored coupling product (Table 1 ). Product formation is thus influenced by the reaction medium. 4. Ally1 ether bonds are particularly easily split; even anionized allyl alcohol is smoothly cleaved ( I : 1, 6 h at 70 C in THP, relative yield 100%) [cq. ( 5 ) ] : DPHLi + C'H=CH--CHr- Q B OLi - DPH-CHr-CH--CH2 + Li2O (5) 5. The relative rates of nucleophilic fission of C-0 bonds by DPHLi decrease in the order Allyl-0> Vinyl-0> Alkyl-0& Phenyl-0-. Many of the ethers included in Table I were treated with benzhydryllithium instead of DPHLi, and the results were qualitatively identical and quantitatively similar. It is probable that nucleophilic ether fission is a characteristic reaction of mesomeric carbanionoids, being caused by the fact that their basicity islower than that ofother organolithium compounds and that their nucleophilicity is high, the latter being made evident by their extremely rapid coupling with alkyl halides[']. Received: July 25, 1973 [Z 897 lE] German version: Angew. Chem. 85.916 (1973) [ I ] P. S d i o r i g ! ~ ~ Ber. . Dcut. Chcm. C e s 43. 1931 (1910): G W i t r q and L. Liihriirrnn. Liebigs Ann. Chem 550, 260 11942): A . L i i ~ / ~ i i i ~ ~ G h~iir~. Wugnrr-I-. Suiij. E Sir(.lcr. and G . Borth. ihid j57. 46 ( 1944): K . %rc<qlrr and H . - G Cellvrr, ihid. 567, 185 (1950). H . Giliii~iii. A. H . H d ~ ( , i r iand . H Hrirt:fclrlr, J. Org. Chem. IY. 1034 (1954): R. L. Li,r\iiiycr and D. F . Po/kirt. J. Amer. Chcm. Soc. 78, 6079 11956). 121 .4.!Ll~ri~r(~Lcr. and LV D i w i i / / i . Angcw. C'hcm. 85. 90 11973). Angcw. Chem. internat. t d i t . / 2 . 7 5 ( 1973):sec also 1 .Lfricr<.Lrrand W T / w w h t i . Licbies Ann. ('hem. 747. 70 (1971). 857 [ 3 ] a ) C . Wirrug and .A Riiclhri, Ltehigs A n n C'hem. 566. I I 1 (1949): G. U'irricg and G. Kolh. C'hem Ber. 93. 1469 (1960): h) 2.1.S. hil~rrose~h and 0.Reiruiziirh Grignard Reactions of Nonmetallic Substances. Pren- P-0 ttcc-Hall. Ncw York. 1954. pp. 961, 1022  a ) Scc c ' . q B. M. MiUioi1or. 1 7 ~Ahad. Nauk SSSR. Otd. Khim. Nauk 1948. 420: C'hctn. Ahstr. 43. 2OX (1949). If. Gi1nt~rii and J . L TOidc. Rcc. T r a r . C'him. Pays-Bas 6Y. 42X (19501: h) S. Sror/(,.\. J . Amer. C'hcm. Soc. 73. 124 (1951) [j] a ) D. WirrcirhC,r<I,D A o h l . and ti. Cilrwt. !. Amcr. C'hcm. Soc. tYO. 5933 (1958): A . G . F h o n c . M . L J o i m . and N. f i . R r i x J. C'hcm. Soc. R 1Y6Y. X94: b) t;. Crrqmrcr. A . C. &m\. and V . H RW\. !. C'. S. Pcrkin I I 1977. ISYX.  0 . 5 h l DPHLi boluttons irsed were frce from ltthttlm salts: they were prepared from 1,l-diphenylethylene and 11-butyllithiumin light petroleum. The reactions were terminated by addition of an excess ofn-butyl bromide [8bI.  The products wcre separated by column chromatography. Their strttctttres were proved by elemental analyses and by spectroscopy. and in some cases by comparison with samples prepared by independent methods. The relatrve ytelds shown in Table 1 were determined by gas chromatography L\ tth thc aid of pure samples. 181 i t ) h / J q / c r . I f r ; j ! w i u i l . /I. h/<,irwr. :tnd 0. S ~ I i ~ r f ~ Llchlg, ~i'. A t i n Chcm. 473. I (1929): hJ G h h r c h a n d 1 . S i d i t , r . C'hciii. Ber. 103. 2744 (1970) Spiro[3.4]octa-5,7-diene[**I By Arinin d r Mrijere and Liirler-Ulrir,h M e j w [ * ] Dedicatrd to Prc$~.s.sor H . Brockmunn 011 14) compound distilled in the process, together with some trrt-butyl alcohol, into a trap cooled in liquid nitrogen and was obtained pure by preparative gas chromatography" 'I. In its 'H-NMR spectrum (CCI,), (2) shows multiplets at r=3.61 and ~ = 3 . 9 1(each 2H, AA'BB' system of the olefinic protons) and at T = 7.79 (6H, cyclobutyl protons). The IR spectrum of (2) is not characteristic and does not accord with that reported by Chiiwrtog/tr and 7itrsch1'l. The longest-wavelength absorption lies at 257 nm, as does that of ( I ) (see Table 1). his 70th birthday Whereas the spiro[n.4]alkadienes ( 1 ) and ( 2 ) are readily accessible by cycloalkylation of the cyclopentadienyl anion by, respectively, 1,2-dibromoethane and 1,4-dibroniobutanel '1, the analogous reaction with 1,3-dibromopropane does not lead t o (2)"l. We report here the preparation and some of the chemical and spectroscopic properties of the hydrocarbon 12). Table I. IJV data of the spiro[n4]alkadtencs f 1 1 - 1 3 ) and of 5.5dimethyl-l..i-cyclopcntadtene[in ethanol. f 2 I i n i~-pentanc]. 11) 12) 13) (13) 223 <zoo <210 <210 6300 ~~ - 257 2700 257 I500 [a] 254 2750 2900 250 ~151 ~ 5 1 [fjl [a] The extinction coefficient found may be too small because ( 2 ) dimcrizcs very rapidly at room temperature. Compound (2) is of interest in comparison with ( I ) and (3) which differ greatly in their behavior in the Diels-Alder reaction['] and on gas-phase pyrolysis[5,'I, and also because of a possible electronic interaction between the x-orbitals of the diene component and the C-C bonding orbitals of the cyclobutane ringf'l. Our starting material was spiro[3.4]octan-5-one (4)["1. On successive bromination in ethylene glycol, dehydrobromination by potassium hydroxide in methanol and hydrolysis of the acetal ( 5 ) this afforded the ketone (6)["] (yield through 3 steps: 54%). this sequence being analogous to Garbisch's general procedure"''. Attempts to prepare the tosylhydrazone of ( 6 1 , and thence (2) by treatment with methyllithi~mI'~l, failed: 1,4-addition of tosylhydrazide to (6) was observed in all these attempts. However, reduction of (6) by aluminum hydridel"1 yielded thealcohol (7") (74%);subsequent treatment with thionyl chloridc in tetrahydrofuranipyridine iit room temperature led to 5-chlorospiro[3.4]oct-6-ene ( 7 b ) (53 %). Dehydrochlorination of ( 7 b ) by potassium tert-butoxide in tetracthylencglycol dimethyl ether (tetraglyme) at room temperature in a vacuum (0.01= torr)"" afforded the diene (2) (yield 67 YO,determined by gas chromatography); this [*] Do/. Dr. A d e Mcijere and Dipl.-C'hcm. L.-L. Mcycr Orgatitsch~C'hemtsclicsInstittit dcr Cniversitat 24 Gi,ttitigcri. M'indau\ucg 2 I<;crni;iny) [**I This work was supported by grants from the Land Niedersachsen and the Fonds der Chemischen Industrie. 858 In its chemical behavior, (2) resembles (3) rather than ( I ) . Pure (2) dimerizes rapidly at room temperature to give (8)"']. 'H-NMR (CC1,) of ('8): T=4.37 (m, 2 H ) ; 4.50 (m, IH); 4.83 (m, IH); 6.78 (m, IH); 7.51 (m, 3H); 8.35 (m, 12H). The half-reaction time for dimerization in dilute solution ( 0 . 8 6 ~in CC14) at 50 C amounts to ca. 2.3h. On treatment with maleic anhydride in benzene (SO C, 5 h), (17) affords the Diels-Alder adduct ( 9 ) [ ' l l (70%; m.p. 86 C; colorless crystals), ' H - N M R (CDC13): r=3.81 ( t , 2H); 6.47 (dd, 2H); 6.79 (m, 2H); 8.22 (m, 6H). Thermal rearrangement of ( 2 ) , which ring strain should cause to be much easier than that of ( I ) and (3)I'"J. has so far been examined only qualitatively. In a flow pyrolysis apparatus at 400°C a 1 :0.8 mixture of the isomeric bicyclo[3.3.0] octadienes (11) and (12) was formed. Thermal decomposition of the dimer (8) led under these conditions to a product mixture of the same composition. ( 1 1 ) and ( I ? ) can be separated by gas chromatography and identified by means of their ' H - N M R spectrall'l.