The catalytic properties of (II) are comparable with those of other rhodium compounds. Thus, the activity of (II) in the conversion of CO with water is 2.8 mole H2/g-atom Rh.h (46 mg (II), 13 ml AcOH, 6 ml HCI, 6 ml H20, 8.4 g NaI, 600 mm, 90~ The conversion was 51% in the carbonylation of methanol in acetic acid using 17.8 mg (II), 20 ml HI, 9.3 ml CH3CH2COOH, and 0.4 ml methanol at 185~ 30 atm for 2 h.

1. 2.

LITERATURE CITED

C. H. Cheng, D. E. Hendriksen, and R. Eisenberg, J. Am. Chem. Soc., 99, 2791 (1977). D. Forster, J. Am. Chem. Soc., 97, 951 (1975).

A STABLE SEMIACETAL NOT CONTAINING ELECTRONEGATIVE

SUBSTITUENTS AT THE CARBON ATOM

P. M. Lukin, A. B. Zolotoi, S. V~ Konovalikhin, S. P. Zil'berg, A. Kh. Bulai, O. A. D'yachenko, L. O. Atovmyan, and O. E. Nasakin

UDC 542.953:547.239.2:547.384

ComDounds with acyclic semiacetal or gem-diol fragments are unstable and may be iso- lated fromsolution only in rare cases [i]. We have prepared (II) with a stable semiacetal fragment according to the following scheme:

H ] R HC6(OH)OCaH7

R R C----O NH2 \3!2--NH2

_ 4 / i-Call,OH 60--65 ~ ~ 5 C ~ N

CN N ---- ---- / \ CN CN

(II, a, b)

C H a i R (III) I-IOCI'I2 N" CN ~ COK - - -~ /=0 Pt=CHs (a), C2H5 Co)

c 'n~

(iv)

The structure of (IIb) was proven by x-ray diffraction structural analysis. The unit- cell parameters for these crystals are: a = 7.932(2), b = 12.860(2), c = 16.282(3) ~, 7 = 113.92(2) ~ , space group P21/b, Z = 4, dcalc= 1.20 g/cm 3. The structure was solved on a RED-4 diffractometer using Cu K s radiation for 1564 reflections by the direct method and full-matrix refinement, R = 0.050. Compounds (IIa) and (IIc) are stable in DMSO-d 6. The ISC NMR spectra of (IIa) and (IIb) were taken on a WH-90 spectrometer at 22.63 MHz with HMDS as the standard. (IIa): 66.2 (CI), 171.8 (C2), 54.2 (C3), 41.5 (C4), 37.7 (CS), 95.1 (C~), 116.0 (C7), 117.2 and 116.2 (gem-dicyano groups). (IIb): 67.8 (CI), 169.6 (C2), 59.3 (C3), 37.9 (C4), 38.1 (C5), 95.2 (C6), 115.9 (C7), 117.1 and 116.3 (gem-dicyano group). The stability of the semiacetal fragment may be a consequence of the diminished activity of the oxygen atom due to coordination of this atom by C 2 [O...C 2, 2.772(2) ~] and carbon atom of the cisnitrile group [O...C, 3.010(2) ~]. We should note that the Michael condensation of l,l,2,2-tetracyanoethane with trans-~, B-unsaturated ketones (III) and acrolein in aqueous ethanol leads to compounds such as (I) [2] and (IV) (proven by x-ray diffraction structural analysis).

Division of the Institute of Chemical Physics, Academy of Sciences of the USSR, Cherno- golovka. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1450- ]451, June, 1986. Original article submitted February 3, 1986.

1318 0568-5230/86/3506-1318 $12.50 �9 1986 Plenum Publishing Corporation

LITERATURE CITED

i. R. Brattle, General Organic Chemistry [Russian translation], Vol. 2, Khimiya, Moscow (1982), pp. 508-510.

2. O. E. Nasakin, P. M. Lukin, A. B. Terent'ev, A. Kh. Bulai, M. I. Shumilin, and B. A. Khaskin, Zh. Org. Khim., 20, 727 (1984).

SYNTHESIS OF COMPLEXES OF 2,2-DIALKYL- AND

2-SPIRO-I-BORAADAMANTANES WITH ALKENYLACETYLENES

Yu. N. Bubnov and A. I. Grandberg UDC 542.91:541.49:547.1'127

l-Boraadamantane and its derivatives are used as starting or intermediate reagents in the preparation of several types of cyclic and adamantane-type compounds [I]. We have de- veloped a two-step method for the synthesis of complexes of previously unknown 2-methy!- and 2~2-dialkyl-l-boraadamantanes (III) and (IV) according to the following scheme:

B I OMe

(~)

R = : H , Me.

7MB ~ Py

IMe

(H) (III) (:V)

At 20~ (I) undergoes monohydrogenation over platinum-group catalysts to form a ~ i:i mixture of bicyclic olefins (II) which are the products of 1,2- and 1,4-addition hydrogen addition to the dienic system (the synthesis of (I) is described in our previous work [I]). Dihydrogenation does not occur in this case. Both isomers of (II) upon hydroborylation using H3B.THF with subsequent heating in THF at 60~ for 2-3 h give complexes (III) in 62- 90% yield, which, upon treatment by pyridine, are converted to adducts (IV). These adducts display stability in the air.

0

(v) ivy)

Spiro compounds (V) and (VI) were synthesized by the same method from 3-methoxy-7- cyclohexenyl-3-borabicyclo[3.3.1] non-6-ene [i].

The structures of (III)-(VI) were indicated by elemental analysis and physicochemical methods including iSC and ::B NMR spectroscopy. The yield of (III), R = H, was 90%, bp 65-66.5~ (1.5 mm), nD 2~ 1.5085. The yield of (III), R = Me, was 62%, bp 62-63.5~ (1 mm) nD 2~ 1.5194. The yield of (IV), R = H, was 76%, mp I13.5-I15~ (from ethanol). Theyieldof (IV), R = Me, was 73%, mp I17-I19~ (from ethanol). The yield of (V) was 89%, dec. above 80% (from THF)t The yie_lld of (VI) was 82%, mp 198-200~ (from THF).

N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1451-1452, June, 1986. Original article submitted February 5, 1986.

0568-5230/86/3506-1319 $12.50 �9 1986 Plenum Publishing Corporation 1319