To our knowledge such activities have not previously been described.

RHC=CX-COOH RCHz-CHX-COOH ( 3 ) ( 4 )

R = H or CH,; X=F, CI, or Br

The behavior of unsaturated a-halocarboxylic acids is depicted in Table 2. With the exception of a-fluorobutyric acid the absolute configurations of the compounds obtained are known.

highly-bridged cyclophanes. We now report the synthesis of [2.2.2.2](1,2,4,5)cyclophane ( 9 ) . Treatment of dimethyl 2,5-dimethylterephthalate (1 )[31 with N-bromosuccinimide gave (2) (colorless needles, m. p. 169 to 171°C; caution! (2) is a potent allergen)'41. The coupling of (2) with 1,4-benzenebis(methanethiol) occurred in 59 % yield to give (3) (colorless prisms, m. p. 158.5-159.5"C). Irradiation of a solution of (3) in trimethyl phosphite, follow- ing the usual procedure for expulsion of sulfur from the mole-

Table 2. Hydrogenation of a,b-unsaturated a-halocarboxylic acids ( 3 ) by Clostridium kluyueri in presence of hydrogen to a-halocarboxylic acids ( 4 ) .

Halocarbox- Amount Product Yield la173 ["I C [.]?J ["I ylic acid ( 3 ) [mmol] f 4 J 1x1 in methanol [3] [giloo mll in methanol

a-Chloroacrylic acid ( 3 a ) 2.0 (R)-a-Chloropropionic acid ( 4 0 ) 91 17.3 k 1.4 0.51 - 13.9 a-Bromoacrylic acid ( 3 b J 1.5 (R)-a-Bromopropionic acid ( 4 b J 86 32.4 k 3.6 0.49 - 27.6

- Z-r-Fluorocrotonic acid ( 3 c ) 2 6 r-Fluorobutyric acid ( 4 c ) 98 12+0.1 2 0 Z-r-Chlorocrotonic acid ( I d ) 0 5 (R)-r-Chlorobutyric acid (4d1 8 3 1 2 7 k 1 . 4 0 42 - 9.7 Z-a-Bromocrotonic acid ( 3 e ) 1.0 (R)-a-Bromobutyric acid f 4 e ) 79 21.6 k 0 . 9 1 . 1 -31.7

The hydrogenation system of C. kluyveri affords the R config- uration. Most of the compounds exhibit a higher rotation than is given in the literature[31. An exception is a-bromobu- tyric acid. As a rule for each mmol of sodium salt of the carboxylic acids, 2.0 g of wet C. kluyveri sediment grown on crotonate was incubated in 10 ml 0.1 M phosphate buffer at pH = 7.0 for I s 2 5 h at 35°C under hydrogen.

Received: November 1 1 , 1974 [Z 126 IE] German version: Angew. Chem. 87, 1 1 1 (1975)

CAS Registry numbers' ( l a ) ? 2345-61-1; ( I b ) , 1609-93-4; ( l c ) , 6213-89-4; ( I d ) , 6213-90-7; ( I P ) . 3791-42-2: ( , ( I ) . 107-94-8; ( 2 h ) . 625-68-3: ( 3 0 ) . 598-79-8: ( 3 h ) . 10443-65-9: ( 3 r ) . 383-85-7: ( 3 d ) . 53993-41-2: ( 3 ~ ) . 5405-34-5: ( 4 0 ) . 7474-05-7: ( 4 h ) . 10009-70-8: ( 4 ~ ) . 433-44-3: ( 4 d ) , 54053-45-1 : ( 4 0 ) . 2681-94-9

[ l ] H . Simon, B. Rambeck, H . Hashimoto, H . Gunrher, G. N o k y n e k , and H . Neumann, Angew. Chem. 86, 675 (1974); Angew. Chem. internat. Edit. 13, 608 (1974). [2] H . Giinrker, H . Haskimoro, B. Rambeck, and H . Simon in H . Dellweg: 3. Symposium Technische Mikrobiologie Berlin. Verlag Versuchs- und Lehr- anstalt fur Spiritusfabrikation und Fermentationstechnologie, Berlin 1973, p. 329.

[3] W G a f l e l d and W G. Galr t to , Tetrahedron 27, 915 (1971).

By Richard Gray and K Boekelheide"] Although cyclophanes with multiple bridges having three or more linking atoms in the bridges are known['', the tris-bridged cyclophanes having only two linking atoms in the bridges, [2.2.2]( 1,3,5)cyclophane and [2.2.2]( 1,2,4)cyclophane, have only been reported recently['l. Because of the strong trans- annular interaction between the aromatic K-electron clouds in these molecules, as evidenced from their spectral and chemi- cal properties, it is of interest to examine other, even more

[*I R. Gray and Prof. Dr. V. Boekelheide[**] Department of Chemistry, University of Oregon Eugene, Oregon 97403 (USA)

['*I V. B. thanks the Alexander von Humboldt Stiftung for the award ofa Senior Fellowship held in residenceat the Institut fur Organische Chemie der Universitat Karlsruhe, 1974-75. [***I This work was supported by the National Science Foundation

C H 2 B r

12)

( 3 ) (41

A

/ I

V

' d C H 3

V

(6), R = CH2OH (7), R = C H = O

(81, R = CH=N-NH-TOS

cule['I, gave ( 4 ) (colorless plates, m.p. 144--145°C) in 69% yield. From the work of Reich and Cram[61, it is known that carbonyl groups attached to one deck of a [Z.S]paracyclophane exert a strong influence directing electrophilic substitution to the pseudogeminal position of the opposite deck. Therefore, as anticipated, chloromethylation of ( 4 ) using chloromethyl methyl ether and aluminum chloride gave (5) (colorless plates, m. p. 189--192°C) in 727, yield. Reduction of (5 ) with diiso- butylaluminum hydride led to (6) (colorless powder, m. p. (dec) > 200°C) in 98% yield. Oxidation of ( 6 ) with activated manganese dioxide['] then gave the corresponding dialdehyde (7) (fine yellow needles, m.p. (dec)>240"C) in 85% yield. Transannular carbenoid insertion reactions of [2.2]paracyclo- phanes have been observed previously by Cram; they provide

Angrw. Chem. inrernar. Edir. 1 Vol. 14 ( 1 9 7 5 ) N o . 2 107

an excellent method for the introduction of bridges consisting of two carbon atoms[']. When (7) was converted into the corresponding bis(tosy1hydrazone) (8) and this was treated with sodium methoxide in T H F followed by irradiation with a sun lamp, conversion to the desired hydrocarbon ( 9 ) occurred in 49 % yield. [2.2.2.2]( 1,2,4,5)Cyclophane ( 9 ) sublimes readily a t 250°C to give tiny, colorless plates [m. p. 350°C; 'H-NMR (CDCI,): a singlet a t 7=4.04 (4H) and an A2Bz pattern at 6.50-7.40 (16H); h,,x(cyclohexane)=248 (&=3610), 294 (sh, 660), and 303nm (1050). The NMR chemical shifts of the aromatic hydrogens of ( 9 ) are at lower field than those of the symmetri- cal [2.2.2]( 1,3,5)cyclophane (t =4.27); this would suggest that the aromatic rings of ( 9 ) are boat-shaped with the -CH groups at the bowsprit positions allowing them to be further apart.

Received: November 26, 1974 [Z 131 IE] German version: Angew. Chem. 87. 138 (1975)

[l] A. J . Hubert, J. Chem. SOC. 1965, 3160; J . Chem. SOC. C 1967, 6, 11 , 13; R. D. Stephens, J. Org. Chem. 38, 2260 (1973). [2] K Boekelheide and R. A. Hollins, J. Amer. Chem. SOC. 95, 3201 (1973); E. A. Euesdale and D. J . Cram, ibid. 95, 5825 (1973). [3] M. Cachia and H. Wakl. Bull. SOC. Chim. Fr. 1958, 1418.

at room temperature to the corresponding isothiocyanati- dateL3]. We tried to overcome the difficulties presented by the silver cyanide method by using trimethylsilyl cyanide as reaction partner. This reagent was recently employed in the synthesis of inorganic and organic cyanides14! The appropriate sulfenyl chlorides["] were allowed to react with trimethylsilyl cyanide at - 10°C in dichloromethane. Exothermic reaction took place and trimethylsilyl chloride was removed under vacuum at 0 "C. The spectroscopic proper-

ties of the thiocyanatidates ( I a)-(1 d) (Table 1) are identical with those described in our previous papers13* 51.

Thiocyanatidates synthesized by the trimethylsilyl cyanide method are distinctly more stable than those obtained by the silver cyanide method. It was possible to isolate tert-butyl- (pheny1)phosphinothiocyanidate ( I d ) as a crystalline solid (m.p. in sealed tube: 38-42°C; rearrangement). ( 1 d) is stable

Table 1. Physical data of the phosphorothiocyanatidates ( / ( I ) - ( / c ) and phosphinothiocyanatidate ( I d ) and their isomerization products. the isothiocyanatidates (2a ) - ( -7c ) and ( Z d ) .

Cpd. R R' 31P-NMR IR [cm - '1 B. p. n 6' CPPml [a1 vP=O vSCN ["Cporr]

(CH3)3CCH20 (CHd3CCH20 - 10.8 1270 2170 + 18.0 I275 2010

(CHJ2CHO (CHd2CHO - 7.8 1270 2173,2185 +21.0 1290 2008

-0-CH Z-CH2-CH(CH3)-0- - 2.0 2150

+ 25.5 1225 2005 (CHd3C CsHs - 73.0 1208, 1235 2185

- 39.0 1210, 1240 2000

+ 27.0

-

68/0.01

65i0.2 ~

- -

~

-

9710.01

- 1.4651

1.4692 -

- - - -

1.5750

[a] &values, H ~ P O I as standard. [b] ( l c ) isomerized to c i s - (2c ) (64%) and trans-f2c) (36%) [ 5 ] .

[4] Satisfactory elemental analyses were obtained for all the new compounds reported. Further, the UV,-IR, NMR, and Mass spectra of all the new compounds are also in agreement with the given structures. [5] K Boekelkeide, I. D. Reingold, and M . Turtle, J. C. S . Chem. Commun. 1973, 406; J . Brukin and W Jenny, Tetrahedron Lett. 1973, 1215. [6] H. J . Reick and D. J . Cram, J . Amer. Chem. SOC. 91, 3505, 3517, 3527 (1 969). [7] J . Atrenburrow, A. F . B. Cameron, J . H. Chapman, R. M . Evans, B. A. Hems, A. B. A. Jansen, and 7: Walker, J. Chem. SOC. 1952, 1094. [8] D. J . Cram, R . B. Hornsby. E. A . Truesdale, H. J . Reick, M . H . Delron, and J . M. Cram, Tetrahedron 30, 1757 (1974).

A New Route to Phosphoro- and Phosphinothio- c yana tidates

By Andrzej Lopusinski, Jan Michalski, and Wojciech J . Sted'] Although intermediate formation of phosphoro- and phos- phinothiocyanatidates ( I ) would appear indispensable to de- scribe many reactions leading to the isomeric isothiocyanati- dates (2)['* 21, it was only recently that we were able to report evidence for the formation of a phosphorothiocyanatidate in the reaction of bis(neopenty1oxy)phosphorylsulfenyl chlo- ride with silver cyanide. The thiocyanatidate isomerizes rapidly

['I Dr. Andrzej topusihski, Prof. Dr. Jan Michalski, and Doz. Dr. Wojciech J. Stec Polska Akademia Nauk, Centrum Badad Molekularnych i Makromolekularnych 90-362 LodZ, Boczna 5 (Poland)

a t room temperature under strictly anhydrous conditions for several days. Starting from the optically active tert-butyl- (pheny1)phosphinothioic acid we succeeded in preparing opti- cally active ( 1 d) which isomerized in the reaction mixture to (2d ) [ I 1 and could be trapped as the optically active N-[tert- butyl(phenyl)phosphinoyl]-N'-cyclohexylthiourea (4)[** ' ] .

The reason for the relatively high stability of ( I d ) is, in the light of our earlier findings on the rearrangement of cyclic phosphorothiocyanatidates, due to steric hindrance, which affects the rate of the SCN --catalyzed SN2(P) isomerization.

[**I Prepared from the corresponding monothioacids [6] or their triethylam- monium salts [7] by action of sulfuryl chloride in dichloromethane (see also eq. (2)). [***I Starting from (3) [S], [a]ho= + 18.5". ( 4 ) was obtained according to eq. (2). [ ( 4 ) : m.p. 162--164°C (ethanol), [a]ho= f53.0" (benzene)].

108 Angen. Ckem. internal. Edit. I Vol. 14 (1975) No. 2