D-Camphoric anhydride

The present method is adapted from that of Loven. The resolution has been carried out with d-a-bromocamphor-TT-sulfonic acid (f-form) 2.3 with /-and d/-malic acids (d- and /-forms) with /-quinic acid and d-tartaric acid (d- and /-forms) and with d- and /-6,6 -dinitrodiphenic acids (d- and /-forms). Methods employing d-benzyimethylacetyl chloride, d-oxymeth-ylenecamphor, /-quinic acid, and d-camphoric anhydride are of theoretical interest only. The d/-amine is not resolved by the active camphor-lo-sulfonic acids or mandelic acids. ... 

A special case of stereoelectivity has been encountered in polymerizing a racemic monomer with an optically active one. Minoura et al. (158) carried out the ring-opening copolymerization of propylene oxide with d-camphoric acid anhydride using diethyl zinc and triethyl amine as catalyst. It was found that the products were alternating copolymers which were optically active. The propylene oxide recovered from the copolymerization system was also optically active. An attempt to incorporate preferentially in a polyamide chain one of the optical antipodes of trans-cyclopropane-1,2-dicarbonyl chloride, by polycondensing this racemic monomer with optically active 1,2-propylene diamine failed (159). 

Let us also mention some asymmetric-selective copolymerizations with propylene oxide (PO) it could be expected that another chiral co-monomer would favor the asymmetric-selection of one of both co-monomers. Tsuruta etal.[ S 2i] reported the asymmetric-selection copolymerization of 3-phenyl-4-tetrahydrophthalic acid anhydride with PO (LXI). Minoura et al [152] described the alternating copolymerization of PO and d-camphoric acid anhydride with diethylzinc triethylamine as optically inactive initiator the... 

In a 3-1., three-necked, round-bottomed flask fitted with a powerful slow-speed stirrer having a Teflon blade, a 500-ml. dropping funnel, and a thermometer arranged to dip into the liquid is placed 588 g. (366 ml., 6 moles) of concentrated sulfuric acid. The flask is surrounded by an ice-salt mixture, the stirrer started, and 1216 g. (1170 ml., 12 moles) of acetic anhydride (Note 1) is added at such a rate that the temperature does not rise above 20° (Note 2). The separatory funnel is removed and 912 g. (6 moles) of coarsely powdered D,L-camphor is added (Note 3). The flask is then closed with a stopper and stirring is continued until the camphor is dissolved. The stirrer is replaced by a stopper, the ice bath allowed to melt, and the mixture left to stand for 36 hours (Note 4). The camphorsulfonic acid is collected on a suction filter and washed with ether (Note 5). After being dried in a vacuum desiccator at room temperature, the nearly white crystalline product weighs 530-580 g. (38-42%). It melts at 202-203° with rapid decomposition and is relatively pure (Note 6). 

Indenopyrene, see Indeno[l,2,3-crf pyrene l//-Indole, see Indole Indolene, see Indoline Inexit, see Lindane Inhibisol, see 1,1,1-Trichloroethane Insecticide 497, see Dieldrin Insecticide 4049, see Malathion Insectophene, see a-Endosulfan, p-Endosulfan Intox 8, see Chlordane Inverton 245, see 2,4,5-T lodomethane, see Methyl iodide IP, see Indeno[l,2,3-crf pyrene IP3, see Isoamyl alcohol Ipaner, see 2,4-D IPE, see Isopropyl ether IPH, see Phenol Ipersan, see Trifluralin Iphanon, see Camphor Isceon 11, see Trichlorofluoromethane Isceon 122, see Dichlorodifluoromethane Iscobrome, see Methyl bromide Iscobrome D, see Ethylene dibromide Isoacetophorone, see Isophorone a-Isoamylene, see 3-Methyl-l-butene Isoamyl ethanoate, see Isoamyl acetate Isoamylhydride, see 2-Methylbutane Isoamylol, see Isoamyl alcohol Isobac, see 2,4-Dichlorophenol Isobenzofuran-l,3-dione, see Phthalic anhydride 1,3-Isobenzofurandione, see Phthalic anhydride IsoBuAc, see Isobutyl acetate IsoBuBz, see Isobutylbenzene Isobutane, see 2-Methylpropane Isobutanol, see Isobutyl alcohol Isobutene, see 2-Methylpropene Isobutenyl methyl ketone, see Mesityl oxide Isobutyl carbinol, see Isoamyl alcohol Isobutylene, see 2-Methylpropene Isobutylethylene, see 4-Methyl-l-pentene Isobutyl ketone, see Diisobutyl ketone Isobutyl methyl ketone, see 4-Methyl-2-pentanone Isobutyltrimethylmethane, see 2,2,4-Trimethylpentane Isocumene, see Propylbenzene Isocyanatomethane, see Methyl isocyanate Isocyanic acid, methyl ester, see Methyl isocyanate Isocyanic acid, methylphenylene ester, see 2,4-Toluene-diisocyanate... 

Procedure 1 Condensation of (-)-menthone and terr-butyl acetoacetate in acetic anhydrid, catalytic amount of sulphuric acid, room temperature, 24 h. The sole, previously described analogous condensation of ( -)-camphor with a-methylmalonic acid required 200 d A. Michael, N. Weiner, J. Chem. Soc. 1936, 58, 680 - 684 B. Eistert, F. Geiss, Chem. Ber. 1961, 94, 929 - 947. 

Beilstein Handbook Reference) AI3-00753 Benzo-a-pyrone BRN 0383644 Caswell No. 259C CCRIS 181 Cinnamic acid, o-hydroxy-, 8-lKtone ois-o-Coumaric acid anhydride Coumarin cis-o-Coumarinic acid lactone Coumarinic anhydride Coumarinic lactone Cumarin EINECS 202-086-7 EPA Pesticide Chemical Code 127301 HSDB 1623 o-Hydroxycinnamic lactone 0-Hydroxyzimtsaure-lacton Kumarin NCI C07103 NSC 8774 Rattex Tonka bean camphor. Used in pharmaceuticals as a flavorant. Crystals mpo 71" bp = 301.7 d O = 0.936 Xm = 273, 311 nm (e = 11200, 6710, MeOH) moderately soluble in H2O, EtOH, more soluble in EtzO, CHCI3, C5H5N. Alfa Aesar Rhodia Inc. Rhodia Organique Fine Ltd. 

A soln. of startg. (+ )-camphor-derived oxazoline in methylene chloride containing 3 eqs. cyclopentadiene, 3 eqs. CaC03, and 1.1 eqs. trifluoroacetic anhydride kept at — 78° for 4 h product. Y 73% (100% endo d.e. 94%). Acetic anhydride and methyl chloroformate were less potent activators. F.e.s. A. Pouilhes et al.. Tetrahedron Letters 30, 1395-8 (1989). 

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