1-Allyl-2-allylthio

Conversion of 5-allylthioimidates into /V-allylthioamides is catalyzed by Pd(Il). 2-Allylthiopyridine (820) is converted into the less stable l-allyl-2-thio-pyridone 821 owing to Pd complex formation[509], Claisen rearrangement of 2-(allylthio)pyrimidin-4-(3//)-one (822) affords the A-l-allylation product 823 as the main product rather than the A -3-allylation product 824[510] The smooth rearrangement of the allylic thionobenzoate 825 to the allyl thiolo-benzoate 826 is catalyzed by both PdCl2(PhCN)2 and Pd(Ph3P)4 by different mechanisms[511],... 

Treatment of 2-methylthiirane with t-butyl hydroperoxide at 150 °C in a sealed vessel gave very low yields of allyl disulfide, 2-propenethiol and thioacetone. The allyl derivatives may be derived from abstraction of a hydrogen atom from the methyl group followed by ring opening to the allylthio radical. Percarbonate derivatives of 2-hydroxymethylthiirane decompose via a free radical pathway to tar. Acrylate esters of 2-hydroxymethylthiirane undergo free radical polymerization through the double bond. 

Mercapto-benzimidazol (und ahnliche ambidente Nukleophile) werden mit Kohlensaure-al-lylestern thermodynamisch kontrolliert am S-Atom angegriffen, wenn man das thiophile Palladium ) als Katalysator einsetzt. Mit 3-Ethoxycarbonyloxy-l-phenyl-propen II erhalt man 2-(3-Phenyl-allylthio)-benzimidazol (III 36%), mit 2 Aquivalenten an II l-(3-Phenyl-allyl)-2-(3-phenyl-allyIthio)-benzimidazol (IV 52%) neben einer geringen Menge l,3-Bis-[3-phenyl-allyl)-2-thiono-2,3-dihydro-benzimidazol (V 7%)378. 

Mercapto-benzimidazol wird von Allyl-bromid in Gegenwart von Natriumhydrogencarbonat zunachst am S-Atom zu 2-Allylthio-benzimidazol (60%) alkyliert. Beim Erwarmen wandert der Allyl-Rest (Claisen-Umlagerung) vom S- zum N-Atom, und man erhiilt l-Allyl-2-mer-capto-benzimidazol (50% Schmp. 115—117°)372. 

Thiazolidine-2-thione, 3-allyl-, 56, 79 2-Thiazohne, 2-allylthio-, 56, 77 2-Thiazoline, 2-benzylthio-, 56, 82 2-Thiazoline, 2-cmnamylthio-, 56, 82 2 Thiazoline, 2 ethylthio, 56, 82 2-Thiazohne 2-mercapto-, 56, 77 2-Thiazoline, 2-methylthio-, 56, 82 2-Thiazohne, 2-(4-phenyl-l-buten-3-yl)-thio-, 56, 78... 

Methyl (allylthio)acetate, CH2—CHCH2SCH2COOCH3 (1). Mol. wt. 146.21. The reagent is prepared I rom allyl bromide and methyl mcrcaptoacetate (83% yield). 

The 3-phenylthieno[2,3-d]pyrimidine-2,4-diones 3b and the corresponding -4-one-2-thiones 4b were converted into the respective 2-allyloxy 139a and 2-allylthio 139b derivatives by reaction with allyl chloride in base (89KGS347). 

Allylthio-3-methyl-2(377)-pyrimidinone 890 yields the 5-allyl-4-thiouracil 891 quantitatively on heating, although the 1-methyl isomer resists rearrangement. 

Thiazol 5-Allylthio-4-cyan-3-hydroxy- E8a, 693 [(NC)2C = C(SK)2+H202 Allyl-Hal]... 

These reactions, coupl with the alkylations of sulfides and selenides, allow the homologation of primary alkyl halides - - - and the transformation of allyl halides to homoallyl halides. A related process, employing 2-methylthio- and 2-allylthio-thiazoline, allows the iodomeAylation (ICH2—) and the iodopropenylation (ICH2CH=CH—) of alkyl halides (Scheme 54).i3iii,i32.i7i... 

Allylthio-methanphosphonsaure-dimethylester 2,4g (0,03 mmol) Allyl-chlormethyl-sulfan und 3,3 g (0,02 mmol) Triethoxyphosphan werden 24 Stdn. auf 110° erhitzt, danach destilliert Ausbeute 3,0 g (67%) Sdp. 77-7870,11 mmol (14,6 Pa). 

Allyl-(2-subst.-l-alkenyl)-sulfan l,9g (0,03 mmol) 2-Butyl-lithium in Cyclohexan gibt man langsam bei 78° zu einer Losung von 6,7 g (0,03 mmol) Allylthio-methanphosphonsaure-dimethylester in THF. Bei -78° werden 2,9g (0,03 mmol) Cyclohexanon zugegeben anschlieBend wird 15 Min. auf 25° und 15 Stdn. auf 50° er-warmt Ausbeute 4,2 g (83°/o). 

H(22)2217>. 4-Allylthio-3-methyl-2(3//)-pyrimidinone is rearranged to the 5-allyl-4-thiouracil... 

Allylthio)-l,2,4-triazin-5(2//)-ones (219) rearrange by palladium(II) catalysis, depending on the substitution pattern of the allylic moiety to 2- (220) or 4-ally l-3-thioxo-3,4-dihydro-l,2,4-triazin-... 

Allylthio-l,2,4-triazin-3(2//)-ones (224) can be rearranged by palladium(II) catalysis only 4-allyl-5-thioxo-4,5-dihydro-l,2,4-triazin-3(2//)-ones (225) were obtained, with (in cases in which R = H in (224)) none of the C-6-alkylated products (Equation (24)) <85T5289>. 

A closely related 2C-T-X compound was also started quite a while later -this was the allylthio homologue of the methallyl material 2C-T-3 or 2C-T-20. Its place in the flow of things is evident from its numbering, 2C-T-16. A mixture of 2,5-dimethoxythiophenol and KOH and allyl chloride in MeOH gave 2,5-dimethoxyphenyl allyl sulfide as a white oil which boiled at 110-125 °C at 0.25 mm/Hg. This, with POCI3 and N-methylformanilide provided 2,5-dimethoxy-4-(allylthio)benzaldehyde which distilled at 140-160 °C at 0.4 mm/Hg and could be recrystallized from MeOH as a pale yellow solid. Reaction of this aldehyde in nitroethane in the presence of ammonium acetate (steam bath for 2.5 h) provided 2,5-dimethoxy-4-allylthio-beta-nitrostyrene as red crystals from acetonitrile. Its mp was 114-115 °C. Anal. (C13H15N04S) C,H. This has not yet been reduced to the final amine, 2,5-dimethoxy-4-allylthiophenethylamine, 2C-T-16. The corresponding amphetamine would be, of course, ALEPH-16. 

A closely related 2C-T-X compound was also started quite a while later Q this was the allylthio homologue of the methallyl material 2C-T-3 or 2C-T-20. Its place in the flow of things is evident from its numbering, 2C-T-16. A mixture of 2,5-dimethoxythiophenol and KOH and allyl chloride in MeOH gave 2,5-dimethoxyphenyl allyl sulfide as a white oil which boiled at 110-125 deg C at 0.25 mm/Hg. This, with POCI3 and N-methylformanilide provided... 

A series of trisubstituted alkenes containing (Z)-allylthio moieties as the key structural units, that is, sodium (Z)-allyl thiosulfates 338, symmetrical di[(Z)-allyl] sulfides 343 and di[(Z)-allyl] disulfides 339 and unsymmetrical diallyl sulfides 341 have been prepared in moderate to good yields via chemical transformations from the acetates of MBH adducts. In addition, it was found that the Sm and a trace amount of I2 could be used for the selective cleavage of the S-S or C-S bonds in sodium (Z)-allyl thiosulfates 338, depending on the substituents (alkyl or aryl group), to give the corresponding... 

The Pd(PhCN)2Cl2 catalyzed Claisen rearrangement of aUyl vinyl ethers has been studied to a lesser extent. The Claisen rearrangement shown in eq 48 proceeds smoothly even at room temperature to give the syn product with high diastereoselectivity. The Claisen rearrangement of 2-(allylthio)pyrimidin-4-(3fl)-one affords the N-1 allylation product as a main product rather than the N-3 allylation product (eq 49). ... 

On reaction with diallyl sulfide and other sulfides containing a reactive allyl group, rearrangement of the sulfilimine originally formed takes place to N-allylthio-N-allyl-/7-nitrobenzenesulfonamide (18) ... 

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