Methoxy-methyl-amine

N-Methyl-N-methoxycarbamoyl chloride made by phos-genation of methoxy methyl amine hydrochloride is a very useful intermediate for the synthesis of N-methoxy ureas herbicides. However, we found the method to be unsatisfactory for the production on a large scale, because of rather low yields and also of technical difficulties. To overcome these problems, we developed a new procedure based on the reaction of phosgene with methoxy methyl amine sulfate as depicted in scheme 124. Sulfuric acid formed is easily removed by decantation (Ref. 177). 

Scheme 124 Preparation of methyl methoxy carbamoyl chloride from the sulfuric acid salt of methoxy methyl amine.

The monomeric structural unit of the 3-alkylpiperidine alkaloids is readily apparent in a number of simple 3-alkylpyridines isolated from marine sponges. In all known examples, the 3-alkyl component of the monomeric unit is attached to a primary amine, methyl amine, methoxy amine, methoxy methyl amine, imine oxide or oxime methyl ether functionality at the distal terminus. 

Purine, 6-methoxy-9-methyl-hydrolysis, 5, 558 Purine, 1-methyl- H NMR, 5, 511 synthesis, 5, 594 Purine, 2-methyl-amination, 5, 542 mass spectra, 5, 519 synthesis, 5, 593 Purine, 3-methyl- H NMR, 5, 511 occurrence, 5, 598 synthesis, 5, 586, 595 Purine, 6-methyl-amination, 5, 542 mass spectra, 5, 519 methylation, 5, 529 oxidation, 5, 539 1-oxide... 

Pyridinium salts, 3-carbamoyl-l-methoxy-covalent amination, 2, 239 Pyridinium salts, cetyl-in electrophotography, 1, 391 Pyridinium salts, 3-chloro-l-methyl-covalent amination, 2, 239 Pyridinium salts, N-cyano-reactions... 

H3C0 hQ) ) O> 0CH3 — (Bis-[4-methoxy-phenyl]-methyl)-amin 71%d.Th. 

Protection of the secondary alcohol as the corresponding methoxy methyl (MOM) ether, followed by removal of the Boc group with ZnBr2 in dichloromethane and acylation of the incipient secondary amine with bromoacetyl bromide in the presence of K2CO3 afforded the bromoacetamide 114 in 86% yield from 113. Treatment of 114 with methanolic ammonia afforded the corresponding glycinamide which was directly subjected to cyclization in the presence of NaH in toluene/HMPA to afford the bicyclic compound 115 in 79% overall yield from 114. Next, a one-pot double carbomethoxylation reaction was performed by the sequencial addition of n-BuLi in THF followed by addition of methylchloroformate, that carbomethoxylated the amide nitrogen atom. Subsequent addition of four equiv of methyl chloroformate followed by the addition of 5 equiv of LiN(TMS)2 afforded 116 as a mixture of diastereomers in 93% yield that were taken on directly without separation. 

S)-1 -Amino-2-methoxy methylpyrroU-dine. (Benzylmethoxymethyl)methyl-amine. 

Amin Tris-[methoxy-methyl]-E14a/2, 202 (Cl - OR) Hydroxylamin... 

Phosphinsaure Ethyl-(methoxy-methyl)- -anhydrid E2, 176 (R2PO —Cl + Amin) Pyrophosphonsaure Ethan- -di-ethylester XII/1, 610 Pyrophosphorigsaure -tetra-ethylester XII/2, 123 (P-O-Kuppl.) XV/2, 235, 424 (Kond.). 

Tris-[2-methyl-propyl]-amin(neutral) Benzyl-dimethyl-amin (pH 10,3) Bis-[3,4-mcthylendioxy-benzyl]-me-thyl-amin (50% H2S04) Dibenzyl-(4-methoxy-benzyl)-amin (50% H2S04)... 

The pyrolysis of [dimethoxy(methyl)silyl]bis(trimethylsilyl)amine350 yields products which can be ascribed to an initial formation of N-(trimethylsilyl)-methoxy(methyl)silanimine (equation 165). The isolated dimers may be formed by the imine dimerization or possibly by an attack of the silanimine on the precursor instead. Additional evidence for the presence of some of the intermediates postulated to account for the results was obtained by a study of the copyrolysis of [dimethoxy-(methyl)silyl]bis(trimethylsilyl)amine and hexamethylcyclotrisiloxane, which yielded a fairly complex mixture of products351. The formation of product 88 most likely proceeds through the unsaturated eight-membered ring silanimine 89 and not by way of meth-ylsilanitrile, although the latter possibility was also considered by the authors (equation 166). 

Figure 4. Depth profile of free amine, methoxy methyl, and primary crosslink density of a 50 y thick blue pigmented melamine formaldehyde crossllnked acrylic copolymer coating that was exposed for two years In Florida. Bars on rhs of graph Indicate concentrations expected In the absence of degradation.

If the /7-position of the amine is blocked by methoxy, methyl, chlorine or bromine groups, the species is stable with respect to dimerisation and higher anodic potentials are required for its further oxidation. However, further decomposition of the tri /7-anisylamine radical cation occurs in the presence of any traces of cyanide ion present in the acetonitrile solution. Primary aromatic amines, like phenols, tend to polymerise upon oxidation unless the o and p positions are blocked. 2,4,6-tri-t-butylaniline in acetonitrile solution yields a fairly stable radical cation which in the presence of water forms 3,5-di-f-butyl-4-amino-2,5-cyclohexadienone. ° ... 

Acenaphthene n-Amyl alcohol Arachidic acid Arachidyl alcohol Benzidine dihydrochloride 2-Butyl octanoic acid Butyloctanol Calcium sulfate Cetylarachidol Cocamine Cocopropylenediamine Cyclodextrin p-Cyclodextrin 1,10-Decanediol 2-Decyl tetradecanoic acid Dihydroxyethyl cocamine oxide Dodecylhexadecanol 2-Hexyl decanoic acid Hydroxypropyl-o-cyclodextrin Hydroxypropyl-P-cyclodextrin Hydroxypropyl-y-cyclodextrin 12-Hydroxystearyl alcohol Isobutyl oleate Kelp Lead phthalate, basic Methoxyethanol 2-Methoxy-5-nitroaniline Methoxy tripropylene glycol acrylate Methylene chloride 2-Octyl dodecanoic acid Oleamine PEG-25 castor oil PEG-30 castor oil PEG-36 castor oil PEG-40 castor oil PEG-200 castor oil PEG-5 hydrogenated castor oil PEG-25 hydrogenated castor oil Polyamide Polysorbate 85 Pyridine Quartz Sodium isopropyl naphthalene sulfonate Soybean (Glycine soja) meal Sucrose Sulfur Tallow amine N-Tallow-1,3-diaminopropane dioleate p-Toluene sulfonic acid Tri methyl amine Tungstic acid Undecylenic acid Vinyl compounds and polymers plastics additive... 

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