Methyl 1-propynyl

Trimethylsilyl-3-rnethylthio-l-propyne, 54 - (32) Trimethyl-silylacetylene, 55 - (32) Bis(trimethylsilyl)acetylene, 56 - (33) 1--Ethoxy-2-trimethylsilylacetylene, 57 - (34) 3-Trimethylsilyl-2 -propyn--l-ol, 58 - (35) 2-Butynoic acid, 59 - (3S) Methyl-1-propynyl sulfoxide,... 

Ci4H3oBe2N2, Methyl-1-propynyl-beryllium-trimethylamine dimer, 37B, 406... 

Dimetbyl-l, 2-tellurazole1 1.7 g (15 mmol) of hydroxylamine O-sulfonic acid are dissolved in 5 ml of water, the solution is cooled to 0°, and 1.23 g (15 mmol) of methyl propynyl ketone are added to the vigorously stirred solution under nitrogen. The solution is stirred for 35 min and 2.5 g (30 mmol) of sodium acetate and 25 ml (l 5 mmol) of a 0.6 molar aqueous solution of potassium telluride are added to the solution over 20 min. The resultant solution is allowed to warm to 20 and is then stirred for 4 h. The reaction mixture is extracted 4 times with 20 ml portions of ethyl acetate and the extract is dried with anhydrous sodium sulfate, filtered, and evaporated to dryness. The residue is sublimed at 70°/0.001 torr and the sublimate recrystallized from acetone yield 0.3 mmol (10%) m.p. 111 . 

Acrylic acid, -(3-benzo[f>]thienyl)-a -mercapto-reaction with iodine, 4, 764 Acrylic acid, o -cyano-y3-(2-thienyl)-ring opening, 4, 807 Acrylic acid, -formyl-in pyridazinone synthesis, 3, 46 Acrylic acid, furyl-rotamers, 4, 545 synthesis, 4, 658 Acrylic acid, 2-hydroxybenzoyl-chroman-4-one synthesis from, 3, 850 Acrylic acid, 5-(l-propynyl)-2-thienyl-methyl ester occurrence, 4, 909 Acrylonitrile... 

The alkynylation of estrone methyl ether with the lithium, sodium and potassium derivatives of propargyl alcohol, 3-butyn-l-ol, and propargyl aldehyde diethyl acetal in pyridine and dioxane has been studied by Miller. Every combination of alkali metal and alkyne tried, but one, gives the 17a-alkylated products (65a), (65c) and (65d). The exception is alkynylation with the potassium derivative of propargyl aldehyde diethyl acetal in pyridine at room temperature, which produces a mixture of epimeric 17-(3, 3 -diethoxy-T-propynyl) derivatives. The rate of alkynylation of estrone methyl ether depends on the structure of the alkyne and proceeds in the order propar-gylaldehyde diethyl acetal > 3-butyn-l-ol > propargyl alcohol. The reactivity of the alkali metal salts is in the order potassium > sodium > lithium. 

The discovery of junipal focused the attention of Sorensen, who had been investigating the occurrence of polyacetylenes in Com-positae, on the possibility that these acetylenes were accompanied by thiophenes. From Coreopsis grandiflora Hogg ex sweet, 2-phenyl 5-(1-propynyl) thiophene (240) was isolated and its structure confirmed by synthesis of the tetrahydro compound, 2-phenyl-5-n-propyl-thiophene. From the root of tansy, the cis and trans isomers of methyl 5-(l-propynyl)-2-thienylacrylate (241) have been isolated. The total synthesis of trans (241) was achieved by reacting junipal with methylcarbethoxy triphenylphosphonium bromide (Wittig reaction) Several monosubstituted thiophenes, (242), (243), and... 

Similarly, dipropynylketone behaves as an aliphatic analog which forms the corresponding 5-methyl-3-(l-propynyl)pyrazoles (70-90% yield) with hydrazine or monosubstituted hydrazines in methyl alcohol at room temperature (74ZOR136) (Scheme 23). 

Chemical Name 17/3-hydroxy-6a-methyl-17-(1-propynyl)androst-4-en-3-one Common Name —... 

Acetylene Compounds. Part XXV. The Occurrence of Methyl-cis-/5-(5-Propynyl-2-thienyl)-acrylate. Acta Chem. Scand. 13, 1185 (1959). 

XXVI. The Synthesis of 5-(l-Propynyl)-2-formyl-thiophene, Junipal, and trans-Methyl-5-(l-propynyl)-2-thienylacrylate. Acta Chem. Scand. 13, 1460 (1959). 

Chemical name N-methyl-4-piperidynyl a-propynyl-cyclopentylglycolate MEDsq- 12 mcg/kg ID50 29 mcg/kg LD50 2,000 mcg/kg D50 20-28 hr C/P ratio 0.8... 

Hethyl-2-butenyl)(2-propynyl)propanedio1c acid, dimethyl ester, 66, 76 Methyl carbamate Carbamic acid, methyl ester (598-55-0), 65, 159 METHYL 4-CHL0R0-2-BUTYN0ATE 2-BUTYNOIC ACID, 4-CHLORO-, METHYL ESTER (41658-12-2), 65, 47... 

Methyl-J-propynyl Sulfoxide from PropynyUithium and Methanesulfinyl Chloride... 

A solution of 1 equiv of o -imino-subsli( tiled or a,a-imino-disnbstituted (S)-2-(methoxymcthyl)-1- [(3-trimethylsilyl-2-propynyl)imino]methyl pyrrolidine and 5-10 equiv of hydrazine hydrate in absolute ethanol (5 mL/mmol) is kept at 20°C or refluxed for several hours, the solution is concentrated under reduced pressure and the oily residue is immediately bulb-to-bulb distilled. 

N12.60% liq, bp 90°(73 mm Hg), ttnl.4450 at 20°. Prepd by reacting at 0° 1-propynyl magpesium bromide with propionohydroxamic chloride in eth. Other preps are given in the same Ref, but the 5-echyl 3 methyl isomer was also formed and it was not possible to separate the two... 

Preparation of N-Cyclohexyl-N-(l-methyl-2-propynyl)-N -p-chloro-phenylurea [27]... 

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