1- PROPYNE, 3-CHLORO

CjHjNS Methyl isothiocyanate CgHjCI 3-Chloro-1-propyne... 

PROPARGYL CHLORIDE PROPYNE, 3-CHLORO- 1-PROPYNE, 3-CHLORO-(624-65-7), 65, 47... 

After the initial claim of the synthesis of an oxirene (by the oxidation of propyne Section 5.05.6.3.1) this system reappeared with the claim 31LA(490)20l) that 2-chloro-l,2-diphenyl-ethanone (110) reacted with sodium methoxide to give diphenyloxirene (111), but it was later shown (52JA2082) that the product was the prosaic methoxy ketone (112 Scheme 97) (the formation of 111 from 110 would be an a-elimination carbene-type reaction). Even with strong, nonnucleophilic bases, (110) failed to provide evidence of diphenyloxirene formation (64JA4866). 

Propiolaldehyde, 3-chloro-, diethyl acetal (8) 1-Propyne, 1-chloro-3,3-diethoxy- (9) (62761-29-9)... 

The cycloaddition of Weinreb amide functionalized nitrile oxide with a range of dipolarophiles has been studied. N-Methoxy-N-methylcarbonocyanidic amide, nitrile oxide 207 (i.e., a nitrile oxide of Weinreb amide type derivative) was generated from 2-chloro-2-(hydroxyimino)-N-methoxy-N-methylacetamide as intermediate and used in situ. Thus, addition of 3-bromo-l-propyne as dipolarophile to this precursor of 207, followed by quenching with triethylamine, gave 5-(bromo-methyl)-N-(methoxy)-N-methyl-3-isoxazolecarboxamide 208 in 55% to 60% yield (367). 

Hatch. L.F. and Kidwell, L.E., Jr. Preparation and properties of 1-bromo-l-propyne, 1.3-dibromopropyne and l-bromo-3-chloro-l-prop3me, / Am. Chem. Soc., 76(l) 289-290, 1954. 

Regardless of whether the Pd-catalyzed coupling or alkyne metathesis is utilized to make PAEs, the critical step is the synthesis of the diiodoarene monomers. In this section some of the more interesting syntheses are showcased. The synthesis of dipropynyldi-tert-butylnaphthalene is shown in Scheme 5. Starting from naphthalene, Friedel-Crafts alkylation with 2-chloro-2-methylbutane gives a mixture of two di-tert-butylnaphthalenes that are separated by crystallization. Iodination of the correct isomer is followed by a Pd-catalyzed coupling of propyne to the diiodide to give the desired l,5-dipropynyl-3,8-di-tert-butyl-naphthalene [56] ready for ADIMET. 

The syntheses of findersine (92a) and its methoxy derivative 92b (28 and 35%, respectively) starting from thallous salts of corresponding 2,4-dihy-droxyquinolines and 3-chloro-3-methyl-l-propyne, on the other hand, did not apparently involve a hydration step. 

Butyllithium, 56 Organozinc reagents, 220 3-Trimethylsilyl-l-propyne, 329 Cross-coupling of alkyl + vinyl groups Iodosylbenzene, 151 Methyl N-benzyloxycarbonyl-a-chloro-glycinate, 186... 

Considerably more work has been reported on the addition of HCI to allenes.73,76 Bismuth trichloride has frequently been added to catalyze these reactions. 1,2-Propadiene affords mixtures of 2-chloro-l-propene, 2,2-dichloropropane,propyne, and l,3-dichloro-l,3-dimethylcyclobutane.75-77... 

Masuyama, Y. Watabe, A. Kurusu, Y. Carbonyl allenylations and propargylations by 3-chloro-l-propyne or 2-propynyl mesylates with SnCl4 and Bu4NI. Synlett 2003,1713— 1715. 

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