Some reactions of 12.alpha.-hydroxymethylabiet-7,-enoic acid

Black, D. K.; Hedrick, Glen W.

doi:10.1021/jo01287a006

Cited by 6 publications

(8 citation statements)

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“…Methyl 12-Acetoxymethylabiet-8,9-enoate (3). Methyl 12-hydroxymethylabiet-7,8-enoate (20.8 grams) in glacial 1 Present address: Hercules Research Center, Wilmington, Del. acetic acid (420 cc.…”

Section: Methodsmentioning

confidence: 99%

“…265-70°C ./1.0 mm., Xm 248 µ (c = 13,600), Xmax 1650 and 1625 cm.™1, NMR signals at 0.79, 0.90 (isopropyl J = 6.5 c.p.s. ), 1.11 (C-10 Me), 1.23 (C-4 Me), 1.98 (acetate Me), 3.60 (ester Me), and signals in the 2.0-2.5 p.p.m. region (C-6 protons) and centered at 3.90 p.p.m.…”

Section: Methodsmentioning

confidence: 99%

“…gave a single peak, t = 7.0 minutes; NMR signals appeared at 0.99, 0.89 and 0.92, 0.82 (doublets for isopropyl group, J = 6.5 c.p.s. ), 1.19 (C-4 Me), 1.02 (C-10 Me), 3.64 (ester Me), doublets centered at 3.76 and 3.98 (J = 12 c.p.s., 5 «-proton), doublets centered at 1.97, 2.15 (J = 12 c.p.s.) and 2.36 p.p.m.…”

Section: Methodsmentioning

confidence: 99%

“…177-9°C ., 7max 1725 (ester C = 0), 1695 cm.™1; no absorption in the ultraviolet region; g.l.p.c. showed a major peak (~95%) at t = 10.5 minutes; NMR signals at 0.97, 0.87 and 0.90, 0.82 (isopropyl doublets), 1.17 (C-4 Me), 0.99 (C-10 Me), 3.63 (ester Me), a broad six-proton signal centered at 1.66 p.p.m. (ring methylenes), two doublets centered at 4.00 and 3.76 p.p.m.…”

Section: Methodsmentioning

confidence: 99%

“…As PART of a program for the preparation of polyols from resin acids (2), methyl 12,14-(2-oxapropano)-abiet-8,9-enoate (1) was obtained by the reaction of formaldehyde with methyl 12a-hydroxymethylabiet-7,8-enoate (2) (3).…”

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confidence: 99%

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Oxidation reactions of methyl 12,14-(2-oxapropano)abiet-8,9-enoate

Black¹,

Hedrick²

1969

J. Chem. Eng. Data

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was cleanly obtained in a 77% yield. When the'reaction was interrupted after 20 hours 2,5-dihydroxycinnamic acid was the major product, 89% yield, accompanied by a little 6-hydroxycoumarin. Excess boron trichloride failed to give any reaction with 2,5-dimethoxycinnamic acid under similar conditions. The use of hydrogen bromide in acetic acid alone gave only decarboxylation to polymeric material; when combined with mercuric chloride, no definable product was obtained.The procedure may have broad utility for the synthesis of coumarins from both o-hydroxy-and o-methoxycinnamic acids, and would be especially valuable for the preparation of hydroxylated coumarins. M ethoxy cinnamic acids are in general more readily obtainable than the hydroxy acids, usually from the Dobner condensation of appropriate benzaldehydes with malonic acid. EXPERIMENTAL 6-Hydroxycoumarin. To an ice-cold solution of 26.7 grams (0.128 mole) of 2,5-dimethoxycinnamic acid (Research Organic Chemicals) in 1 liter of chloroform was added 100 grams (0.4 mole) of boron tribromide, dropwise, with stirring. The yellow solution underwent a series of color changes, eventually becoming orange-red. After one hour, the ice bath was removed and the mixture was allowed to stand for 48 hours at room temperature. The mixture was cooled in ice, and 500 ml. of ice water was added cautiously with stirring. After 30 minutes, the mixture was extracted with ethyl acetate. The organic extract was dried over magnesium sulfate and evaporated in vacuo. The solid residue was stirred with 150 ml. of 5% sodium bicarbonate for 2 hours. The product was collected, washed with water and ether, and dried to leave 16.0 grams (77%) of pale yellow crystals, m.p. 247-48°C .; lit. (1) m.p. 248-50°C. The infrared spectrum was identical with material prepared by the method of Sastri et al. (3).2,5-Dihydroxycinnamic Acid. The reaction was conducted at twice the scale described above, but was worked up after 20 hours. After treatment with ice water, the resulting solid material was collected by filtration. The chloroform layer from the filtrate yielded only a trivial amount of 6-hydroxycoumarin. The filter cake was extracted with several portions of ethyl acetate, dried over magnesium sulfate, and evaporated in vacuo to leave 41.5 grams (89%) of 2,5-dihydroxycinnamic acid, m.p. 197-9°C .; lit. (2) m.p.207°C.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

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Oxidation reactions of methyl 12,14-(2-oxapropano)abiet-8,9-enoate

Black¹,

Hedrick²

1969

J. Chem. Eng. Data

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Polymers from 12 α‐hydroxymethylabiet‐7,8‐enoic acid and vinyl 12 α‐hydroxymethylabiet‐7,8‐enoate

Saga

Marvel

1969

J. Polym. Sci. A‐1 Polym. Chem.

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12 α‐Hydroxymethylabiet‐7,8‐enoic acid has been homopolymerized by melt condensation, and a partially crystalline polyester has been obtained. Vinyl 12 α‐hydroxymethylabiet‐7,8‐enoate has been prepared from 12 α‐hydroxymethylabiet‐7,8‐enoic acid by vinyl interchange with vinyl acetate and has been homopolymerized, copolymerized with vinyl chloride, vinyl acetate, butadiene, and acrylonitrile, and terpolymerized with styrene and acrylonitrile. Polymers thus obtained have been characterized.

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