Science to 20,000 subscribers is expected initially, at an annual subscription price of $24. Further marketing ef forts will be made this spring and summer. (Subscription information is available by writing Issues in Sci ence & Technology Policy, National
istry professor Roy A. Olofson at Pennsylvania State University in single-crystal x-ray studies. The McNeil researchers used sodium hexamethyldisilazide to reconvert the erythro compound to the cisoxaphosphetane and the threo com pound to the trans-intermediate. On warming of the ylide-benzaldehyde reaction mixture to —25 °C, peaks of oxaphosphetanes shrank at the same rate as the peak for triphenylphosphine oxide grew. But at the end, the ratio of cis- to transoxaphosphetane was close to 1:1. The ratio of cis- to trans-olefin pro duced was 1.5:1, which did not re flect the original 3.8:l-ratio of iso meric oxaphosphetanes. By contrast, treatment of the Wittig reagent with hexanal gave a 5.8:l-mixture of cisand trans-oxaphosphetanes, which yielded in turn a 5.8:1-mixture of cis- and trans-olefins. Maryanoff, Mutter, and Reitz con clude that in the presence of lithium, the c/s-4-phenyloxaphosphetane reacts preferentially to form olefin product, and that there is a competi tive equilibration of cis- and transoxaphosphetanes, possibly via re versible interconversion of oxaphos phetanes and starting material. Thus, they say, the relative stereochemi cal preference for cis- and transolefins in the Wittig reaction may be dictated not by what happens during reaction of aldehydes and ylides, but by what can happen to the oxaphosphetanes afterwards. D
Academy of Sciences, 2101 Constitu tion Ave., N.W., Washington, D.C. 20418.) The projections are for an eventu al circulation of 40,000, allowing the journal to reach a breakeven point in four to five years. D
Wittig reaction mechanism confirmed Chemists at McNeil Pharmaceutical, Spring House, Pa., have observed directly the cis- and trans-oxaphosphetanes long suspected to be inter mediates in the Wittig reaction [/. Am. Chern. Soc, 106, 1873 (1984)]. Their findings both confirm cur rent views of the mechanism of the reaction and shed new light on what governs amounts of cis- and transolefin products that result. Organic chemists Bruce E. Maryanoff and Allen B. Reitz worked with nuclear magnetic resonance spectroscopist Martin S. Mutter to follow phosphorus-31 spectra of re action mixtures of phosphorus ylides and aldehydes. They resolved peaks corresponding to cis- and transoxaphosphetanes at 145.8 MHz. One reason for their success is that previ ous workers were limited to the low er resolution of 40.5 MHz. Even at 145.8 MHz, the two baseline-re solved peaks are only 2.4 ppm apart. A second reason for their success is that peaks from the butylidenetriphenylphosphorane they used are farther apart t h a n those of the
ethylidene derivative other workers studied. The McNeil chemists treated b u t y l t r i p h e n y l p h o s p h o n i u m bro mide with lithium hexamethyldi silazide to generate the Wittig re agent and reacted this with benzaldehyde at —78 °C. They observed peaks for cis- and frflns-3-propyl2,2,2,4 - tetraphenyl-l,2-oxaphosphetane in a ratio of 3.8:1. They assigned peaks to the two isomers by two methods. First, they ran the reaction with sodium hexa methyldisilazide. This lithium-free technique is known to give almost entirely cis-olefin, which must come from cis-oxaphosphetane, whose sin gle peak they saw. In the second method, they added hydrogen bro mide to the reaction mixture. This reaction, discovered by organic chemistry professor Manfred Schlosser of Lausanne University, Switzer land, yielded erythro- and threo-1hydroxy-1 -phenyl - 2-pentyltriphenylphosphonium bromides in a 2.6:1 ratio. The structure of separated threo isomer was verified by chem
NMR reveals Wittig reaction intermediates H
/ ' 3 V I ' 2 V ' *2
, DΒ rΓ wΘ
© (C 6 H 5 ) 3 PCH 2 CH 2 CH 2 CH 3 6 5 3 2 2 2 3
Lithium hexamethyldisilazide foMowedby
benzaldehyde
C = C
C=C X ^ 6 ' '5
l·
/ρ Η \ Ρ_θ 1^β π 5/3; γ » J 1 / \ C6H5 CH3CH2CH2
Sodium hexamethyldisilazide
/C6H5
V
it
Hydrogen bromide
i3\^ri2wn2
Î*
(CeH5)3P-0
J_J^ Cn3Cn2CH2 Hydrogen I bromide I
·ς=± CeH5
I Sodium I hexamethyldisilazide
C6H5
H-I-OH H-|-P(CeH5)3 CH2CH2CH3
30
March 26, 1984 C&EN
(C6H5)3P=CHCH2CH2CH3
(CeH5)3P-|-H CH2Cn2Cn3
C e H 5 CHO
was $4.00. As a result, 1984 dues of $65 are $14 lower than they would have been with the full escalation. Assuming that there would have been no loss of membership because of the higher dues, this means a cumulative loss of $4.2 million in dues revenues over these five years. The continuing decrease in the percentage of members paying full dues has been caused in part by a rapid rise in the number of emeritus members, who pay no dues. The total number of members paying no dues has risen from about 11,000 in 1979 to about 19,000 in 1984. And in 1983 (the last year for which full data are available) only 877c of those paying dues were paying at the full rate. The other 13% were student and retired members who pay at half rate. The combined impact of relatively low annual dues increments and the increase in members paying less than full dues has been quite profound. Between 1977 and 1983 the cost of living index rose 78%. But the increase in dues revenue per member was only 47%. Under a new funding policy, known as the General Fund Income Policy (GFIP) and implemented by ACS this year, dues-supported programs are supposed to break even. Nonself-supporting programs that are principally of benefit to members are funded 100% by dues. And
programs in this category that are principally of benefit to the discipline or profession of chemistry are funded 50% by dues and 50% by the reserves of the society. For 1984 all of these nonselfsupporting programs are budgeted at a total of $9.3 million, with $7.4 million of this being the dues revenues and the other $1.9 million coming from reserves. Of the actual dues monies, 33% is allocated to C&EN, local sections, and divisions. Another 8% is needed to cover membership records and local section and division dues collection. The other 59% is budgeted to provide various membership services (22%); to support programs in public affairs (4%), public relations (8%), education (7%), professional relations (7%), and other membership areas (4%); and to cover the costs of liaison with board and council committees (6%) and of various awards activities (1%). As Dixon points out in his message to councilors, the $1.9 million from reserves budgeted for these programs exceeds the return on reserves derived from the ACS investment program. It therefore represents a decline in the society's purchasing power. And, as the B&F chairman stresses, a solid reserve situation is essential both for the overall financial stability of the society and to provide the basis for financing new and special projects.
He explains that the transition of Chemical Abstracts Service from strictly printed publications to an operation that also offers on-line service is a good example of a project that could not have been accomplished without the assistance of the society's reserves. Under GFIP, dues revenues committed to supporting programs at both the 100% and 50% levels are not to exceed total projected dues income. In the approved budget for 1984 this provision is not met. Projected expenses exceed expected dues revenues by about $200,000. And this deficit persists despite some substantial cutbacks in the budget proposed originally. Among programs trimmed are some in professional services, education, public affairs, and public relations. GFIP calls for self-supporting programs—that generate their own revenues—to contribute to the reserves at levels set by the ACS Board of Directors. For instance, the goal for the Books & Journals Division is an amount equivalent to 6.1% of the division's expenses. Hence, in principle, the society's reserves should each year be increased by such inputs from the self-supporting programs as well as by revenues from ACS's investment program. The only decrease should be due to the distribution of reserves to programs jointly funded by dues. D
Guide to April local section meetings featuring ACS tour speakers As a service to society members and the public, C&EN publishes from fall to spring monthly guides to ACS tour speaker appearances at upcoming local section meetings. For general information about these events, which are open to all inter-
ested persons, consult the alphabetical listing of cities and their corresponding local sections along with the topic/ speaker key. For additional information, contact the local section or the ACS Speaker Service at (202) 872-4613.
Meeting city Local section
Meeting city Local section
Date (April) Topic code
Ada, Ohio Northwest Centra! Ohio Aiken, S.C. Savannah River Appleton Wis. Northeast Wisconsin Auburn, Ala. Auburn Binghamton, N.Y. Binghamton Cedar Falls, Iowa Iowa Charleston, S.C. South Carolina
13/D 26/H 26/G 4/E 3/K 25/N 25/H
Meeting city Local section Charleston, W.Va. Kanawha Valley Chattanoogajenn. Chattanooga Cumberland, Md. Western Maryland Dayton, Ohio Dayton Decatur, III. Decatur-Springfield Erie, Pa. Erie Flint, Mich. Flint
Date (April) Topic code) 5/I 26/A 2/I 16/D 12/L 24/M 10/D
Date (April) Topic code)
Ft. Wayne, Ind. Northeastern Indiana Grand Rapids, Mich. Western Michigan Greenville, Pa. Penn-Ohio Border Houghton, Mich. Upper Peninsula Huntington, W.Va. Central Ohio Valley Idaho Falls, Idaho Idaho Kingsport, Tenn. Northeast Tennessee
12/C 25/G 27/Q 27/G 4/I 2/J 3/E
Meeting city Local section Laramie, Wyo. Wyoming Macomb, III. Quincy-Keokuk Mansfield, Pa. Corning Marietta, Ohio Upper Ohio Valley Memphis Memphis Mentor, Ohio Northeastern Ohio Midland, Mich. Midland
Date (April) Topic code) 5/J 13/F 2/K 3/P 24/A 25/M 9/C
March 26, 1984 C&EN
35
