Synthesis and Epoxidation of Bis( 2-cyclopentenyl) Carbonates JOHN W. LYNN, ALEX E. BRODHAG' and SAMUEL W. TINSLEY Research and Development Dept., Union Carbide Chemicals Co., South Charleston, W. Va.
BIS(~-CYCLOPENTENY)
CARBONATE, previously unreoorted. was DreDared bv three different methods: . . ester:exchange between 2-cyclopentenol and diethyl carbonate, phosgenation of potassium 2-cyclopentenylate, and reaction of sodium carbonate with 2-cyclopentenyl chloride (3,4 ) . T h e pure carbonate was observed t o undergo rapid decomposition to C 0 2 , 2-cyclopentenol, and cyclopentadiene a t about 100°C. Epoxidation was effected by treatment with peracetic acid in ethyl acetate (1) t o yield a new diepoxy carbonate, bis(2,3-epoxycyclopentyl)carbonate. Similar compounds have been reported previously ( 2 ) .
(1) Frostick, F.C., Phillips, B., Stacher, P.S., J . A m . Chem. SOC. 81,3350 (1959). (2) Heiberger, C.A. (to Ohio-Apex Co.), British Patent 666,560, 1952. (3) Kukui, K., Yoneda, S., Takayama, H., Ketano, H., Kugyo Kagaku Zasshe, 63,2146 (1960). (4) Mueller, A.C., Shohad, E.C., (to Shell Development Co.), U. S. Patent 2,795,572 (1959).
Table I. Synthesis and Epoxidation of Bis(2-cyclopentenyl) Carbonates %, Calcd.
Compound Bis(2-cyclopentenyl) carbonate Bis(2,3-epoxycyclopentyl)carbonate All temperatures are uncorrected.
Formula C iiH 1 4 0 3 CiiH,aOj
B.B. o/mm."
C
8010.5 12110.09
68.02 58.40
Present address, Chemical Abstracts Service, Ohio State University, Columbus 10, Ohio.
70, Found
H 7.27 6.24
C
H
67.81 58.61
7.40 6.21
RECEIVED for review March 4, 1963. Accepted March 22, 1963.
Polyol Esters of 3-Butenoic Acid JOHN W. LYNN and RICHARD 1. ROBERTS Research and Development Dept., Union Carbide Chemicals Co., South Charleston, W. Va.
S E V E R A L GLYCOL and triol esters of 3-butenoic acid were prepared as intermediates to epoxy resins and for evaluation as reactive plasticizers for vinyl chloride resins.
titanium tetralkylate catalyst. T h e use of an acidic catalyst (Method B) caused partial isomerization of the 3-butenoate system t o be conjugated crotonate system. Physical
Table I. Polyol Esters of 3-Butenoic Acid: (CH?= CHCHLOd,R B.P.," Method C./Mm. -CH,CH>A 97 2 1.4469 -CH?€HCH~ B 90 1.5 1.4422 -CH,CH(C?H,)€HC~HB 129 1.5 1.4483 -cH&H(cH~)~cH~B Residue 1.4645 CHICH2C(CH2-)3 A 170 1.5 1.4634 "All boiling points are uncorrected. 'Based on saponification.
R
T o date, only mono-lower alkyl esters of this acid have been reported. The esters were prepared by direct esterification of 3-butenoic acid (Method A) in the absence of catalyst and also by transesterification of ethyl 3-butenoate using a VOL. 8, No. 3, JULY 1963
%, Calcd.
Purity' d2?
%
Yield
C
1.0532 1.0237 0.9744 1.0642 1.0598
99.5 99.4 99.7 97.3
YU
60.59 62.25 68.05 63.8 63.9
...
86 92 93 77.4
H 7.12 7.6 9.28 7.74 7.70
%, Found,
C 60.65 62.22 68.46 63.2 64.02
H 6.88 8.0 9.15 7.62 7.58
properties for the several poly01 esters of 3-butenoic acid are tabulated and method of preparation are given in Table I. RECEIVED for review March 13, 1963. Accepted March 22, 1963. 445
