Synthesis of imidate hydrochlorides by reaction of ethyl chloroformate with amides and thionamides

Suydam, Fred H.; Greth, Warren E.; Langerman, Neal

doi:10.1021/jo01254a009

Cited by 18 publications

(6 citation statements)

References 3 publications

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“…Journal of the American Chemical Society / 93:24 / December /, 1971 " Av and Tc are given for the methylene protons only; VI measured neat; V, 50%CH2C12; IV, 50%CHC13. 6 Reference 2; data from E.…”

Section: Resultsmentioning

confidence: 99%

“…Dimethylaminotrimethylstannane was prepared by lithioamination of trimethylchlorostannane, bp 125-127°( lit.5 126°). Carbonoxysulfide was obtained from the reaction of thioacetamide with ethyl chloroformate 6 Trimethylsilyl insertion products were prepared by addition of S-Trimethylstannyl dimethylthiocarbamate (VII) was prepared by reaction of COS with dimethylaminotrimethylstannane; mp 40-43°(lit.8 40°).…”

Section: Methodsmentioning

confidence: 99%

“…Except for the trans (1,4) adduct 5, which is a common product of both series, each product can arise from only one biradical, and may be designated as belonging to the erythro or to the threo series. 6 If any biradical were to be re-formed from one of the (1,2) cycloadducts it should be, with overwhelming probability, the same biradical from which the adduct was originally formed, for only so can the stabilization belonging to an allylic cyclopentenyl radical and an -chloroalkyl radical be attained. Because the only remaining question of structural assignment in these (5) Erythro and threo designations are defined by regarding the "free radical" carbon atoms on the two asymmetric centers as corresponding groups, and considering that F corresponds to H in the l,2-dichIoro-l,2-…”

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confidence: 99%

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Hindered rotation in some organometallic carbamates, thiocarbamates, and dithiocarbamates

Yoder¹,

Komoriya²,

Kochanowski³

et al. 1971

J. Am. Chem. Soc.

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Hindered rotation in systems of the type R'YC(=X)NR2, where X,Y = 0 , O ; 0,s; S,O; S,S; R = CHI, CzH6; R' = CH3, Si(CH&, Sn(CH3)3, has been investigated by variable temperature nmr spectroscopy. Rotational parameters were calculated by the total line shape and intensity ratio methods. Effects of substituent groups X, Y, and R' on the free energy of activation are discussed in terms of their effect on the relative importance of the contributing resonance structures.lthough the synthetic aspects of the insertion of (14) M. T. Rogers and . I .

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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confidence: 99%

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Hindered rotation in some organometallic carbamates, thiocarbamates, and dithiocarbamates

Yoder¹,

Komoriya²,

Kochanowski³

et al. 1971

J. Am. Chem. Soc.

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“…All of the compounds 1 − 40 listed in Figure were synthesized according to Scheme . The following compounds were synthesized by published procedures: 2( R )-[2-(carbobenzoxy)aminoacetylamino]-4-methylpentanoic acid, 2( R )-(carbobenzoxy)amino-4-methylpentanoic acid p -nitrophenyl ester, N -( tert -butoxycarbonyl)-1,3-diaminopropane, N -( tert -butoxycarbonyl)-1,4-diaminobutane, N -( tert -butoxycarbonyl)-1,5-diaminopentane, N -( tert -butoxycarbonyl)-1,6-diaminohexane, ethyl propionimidate hydrochloride, ethyl butyrimidate hydrochloride, ethyl valerimidate hydrochloride, butyramide, and valeramide Alkylation of cis -(−)-(2 R ,6 R ,11 R )- N -normetazocine with methyl (1 S ,2 R )-2-(chloromethyl)-1-phenylcyclopropanecarboxylate afforded methyl 1( S )-phenyl-2( R )-[(8-hydroxy-6( R ),11( R )-dimethyl-1,2,5,6-tetrahydro-4 H -2( R ),6-methanobenzazocin-3-yl)methyl]cyclopropanecarboxylate (MPCB) that was hydrolyzed to the corresponding 1( S )-phenyl-2( R )-[(8-hydroxy-6( R ),11( R )-dimethyl-1,2,5,6-tetrahydro-4 H -2( R ),6-methanobenzazocin-3-yl)methyl]cyclopropane-carboxylic acid .…”

Section: Chemistrymentioning

confidence: 99%

Nonpeptide Analogues of Dynorphin A(1−8): Design, Synthesis, and Pharmacological Evaluation of κ-Selective Agonists

et al. 2000

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Two novel series of kappa opioid receptor agonist analogues of MPCB-GRRI and MPCB-RRI, hybrid ligands of MPCB ((-)-cis-N-(2-phenyl-2-carbomethoxy)cyclopropylmethyl-N-normetazocine ) and of the C-terminal fragments of dynorphin A(1-8), have been synthesized. The critical functional groups of the peptide fragments of hybrid compounds were maintained, and the binding affinities and selectivities for compounds 1-40 to mu, delta, and kappa opioid receptors were analyzed. Compounds 15 and 16, MPCB-Gly-Leu-NH-(CH(2))(n)()-NH-C(=NH)-C(4)H(9) (n = 5, 6), displayed high affinity and selectivity for kappa opioid receptors (K(i)(kappa) = 6.7 and 5.3 nM, K(i)(mu)/K(i)(kappa) = 375 and 408, and K(i)(delta)/K(i)(kappa) = 408 and 424, respectively). Since kappa agonists may also cause psychotomimetic effects by interaction with sigma sites, binding assays to sigma(1) sites were performed where compounds 15 and 16 showed negligible affinity (K(i) > 10 000). Compounds 15 and 16 were further characterized in vivo and showed potent antinociceptive activity in mouse abdominal constriction tests (ED(50) = 0.88 and 1.1 mg/kg, respectively), fully prevented by nor-BNI. Thus, these novel analogues open an exciting avenue for the design of peptidomimetics of dynorphin A(1-8).

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“…Furthermore, N-deprotection of N -sulfinyl imidates leads to the corresponding imidates and their salts which have been known for nearly a century but for which only one general direct preparative method exists. This method of Pinner involves the synthesis of the imidate hydrochloride salt from the appropriate nitrile and alcohol with anhydrous hydrogen chloride . Several other synthetic methods of specific imidates have been reported .…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Synthesis of α-Alkylated N-Sulfinyl Imidates as New Chiral Building Blocks

et al. 2009

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Alpha-alkylation of N-sulfinyl imidates, prepared via condensation of tert-butanesulfinamide with ortho esters, led to alpha-substituted N-sulfinyl imidates in good-to-excellent diastereomeric ratios (dr up to >99:1) and yields. Deprotection of the alkylated N-sulfinyl imidates gave access to the corresponding imidate hydrochlorides in outstanding yields. These imidate hydrochlorides proved to be excellent intermediates for an easy transformation to chiral amides in good yields and enantiomeric excess upon simple heating in chloroform. Hydrolysis of the alpha-benzylated imidate hydrochlorides afforded the corresponding chiral esters with >95% ee.

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Synthesis of imidate hydrochlorides by reaction of ethyl chloroformate with amides and thionamides

Cited by 18 publications

References 3 publications

Hindered rotation in some organometallic carbamates, thiocarbamates, and dithiocarbamates

Hindered rotation in some organometallic carbamates, thiocarbamates, and dithiocarbamates

Nonpeptide Analogues of Dynorphin A(1−8): Design, Synthesis, and Pharmacological Evaluation of κ-Selective Agonists

Asymmetric Synthesis of α-Alkylated N-Sulfinyl Imidates as New Chiral Building Blocks

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