Preparation and crystal structures of trans-methyl meso-hydrobenzoin phosphite and phosphate

Abstract

The transesterification of trimethyl phosphite with meso-hydrobenzoin has been found to lead to the single isomeric product, trans-methyl meso-hydrobenzoin phosphite. The phosphite has been converted by ozonolysis to the analogous trans-methyl meso-hydrobenzoin phosphate. Single-crystal X-ray diffraction studies have been completed for both compounds. The phosphite, CisHisPCh, crystallizes in space group P2|2i2i with cell dimensions a = 9.924 (3), b = 5.969 (1), c = 23.225 (5) A, and Z = 4. The phosphate, C15H15PO4, crystallizes in space group Pna2\ with a = 18.559 (4), b = 6.609 (1), c = 23.614 (5) A, and Z = 8. A comparison of the structural features of the phosphite and phosphate is reported. The results show that P-O bond lengths are longer and the O-P-O angles smaller in the phosphite than in the corresponding phosphate.

The structure of the imidazolium salt of 2-hydroxy-1,3,2-dioxaphospholane 2-sulphide

“…The O(2)--P-O(3) ring angle of 96.6 (1) ° is similar to the values found for other 1,3,2-dioxaphospholanes (Steiz & Lipscomb, 1965;Chiu & Lipscomb, 1969;Newton, Cox & Bertrand, 1966;Boer, 1972;Newton & Campbell, 1974;Mikotajczyk et al, 1976;Wieczorek et al, 1976). This angle is over 5 ° smaller than that found in six-membered cyclic compounds containing phosphorus: the 1,3,2-dioxaphosphorinanes (C ameron, Gatdecki & Karolak-Wojciechowska, 1976;Cameron & Karolak-Wojciechowska, 1977).…”

“…Discussion. The five-membered phospholane ring is usually described as non-planar (Steiz & Lipscomb, 1965;Chiu & Lipscomb, 1969;Newton, Cox & Bertrand, 1966;Lee, Goodacre & Peake, 1970;Naumov, Siemashko, Zawialow, Tscherkhasov & Grishyna, 1973;Saenger & Eckstein, 1970;Swank, Caughlan, Ramirez & Madan, 1967;Coulter, 1973;Newton & Campbell, 1974;Miko|ajczyk et al, 1976;Andfianov, Kalinin & Struchkov, 1977;Wieczorek et al, 1976).…”

The structure of monopotassium phosphoenolpyruvate

“…The enolic C(1)-O(13) is 1.374A, significantly shorter than the 1.43 A in PEP.CHA, suggesting partial double-bond character for the bond. The P-O(13)-C(1) angle (126.8 °) is also significantly different from that in PEP.CHA (121.2 °) and from the average (120.0 ° ) for the P-O-C angle in phosphate monoesters (Newton & Campbell, 1974). C(2)-C(1)-O(13) is only 111 °, which is considerably less than the standard value of 120 ° around an sp 2 C atom.…”

The imidazole complex of 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane 2-sulphide

“…We report here the X-ray analysis of the imidazole complex (see Introduction) of 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane 2-sulphide (Ig). The five-membered dioxaphospholane ring has been found to be non-planar in all previous investigations (Steitz & Lipscomb, 1965;Chiu & Lipscomb, 1969;Newton, Cox & Bertrand, 1966;Wieczorek, Karolak- Golifiski, Bartczak, Mikotajczyk & Witczak, 1976;Saenger & Eckstein, 1970;Mikotajczyk, Witczak, Wieczorek, Bokiy & Struchkov, 1976;Andrianov, Kalinin & Struchkov, 1977;Newton & Campbell, 1974;Bentrude & Hart-Wan Tan, 1976). The dioxaphospholane ring in (Ig) displays a half-chair conformation [distances from the best least-squares plane: P 0.017, 0(2) 0.121, C(2) -0.214, C(1) 0.230, 0(3) -0-153 A] with C(1) displaced more than C(2) from the plane defined by P, 0(2) and 0(3).…”

“…The C-O bond lengths of 1-491 (5) and 1.479 (5) ,~ in (Ig) are in A value of about 120 ° has been observed for the P-O-C angles in a large number of acyclic phosphate esters (Newton & Campbell, 1974). In contrast to this are the P-O-C ring angles of 111.1 (3) and 111.0 (3) ° in (Ig).…”