Benzyliden methylamine

C. Miscellaneous.—Treatment of the phosphonium bromide (114) with one equivalent of butyl-lithium gave triphenylphosphine and benzylidene-methylamine via a Hofmann-like decomposition, whereas reaction with two equivalents of butyl-lithium resulted in the production of butyltriphenyl-phosphonium bromide. ... 

Only a few examples of the [3 + 2] cycloaddition of thiocarbonyl ylides with C=N compounds have been reported so far. By comparison with aldehydes, imines are poor dipolarophiles. For example, Al-benzylidene methylamine and adamanta-nethione (5)-methylide (52) produce 1,3-thiazolidine (129) in only 13% yield (163). An alternative and efficient approach to 1,3-thiazohdines involves the [3 + 2] cycloaddition of azomethine ylides with thiocarbonyl compounds [cf. (169)]. 

Ethyl trifluoroacetoacetate (3.0 g. 16.2 mmol) and A-(benzylidene)methylamine. V-oxide (1 2.6 g. 19.4 mmol) were refluxed in toluene for 24 h. After evaporation of the toluene, the crude product was filtered on a silica gel column, and the isoxazolidinc obtained by crystallization from cyclohexane yield 3.36 g (65%) mp 94-96 C. 

Ester-stabilized azomethine ylides 76 (R = MeO, EWG = COOR ) show a high reactivity to imines such as 2-phenyl-1-azirine and Af-benzylidene-methylamine, cycloadduct 220 being obtained in the former case (82LA2146). 

Equimolar amounts of N,N-dimethylcarbamylisothiocyanate and benzylidene-methylamine in ether allowed to stand 1 hr. at room temp, in a closed flask 2-dimethylamino-5-methyl -6-phenyl -5,6-dihydro-4H-l, 3,5- thiadiazin-4-one. Y 82%. F. e., prepn. of carbamyltbiocyanates, RgNCO-S-C = N, and related reactions, s. J. Goerdeler and D. Wobig, A. 757, 120 (1970). 

A kinetic study of the reaction of parasubstituted A-benzylidene methylamines with dialkyl phosphonates reveals that below the isokinetic temperature P (where for a given azomethine the rates of addition for the different phosphonic acid diesters are equal), the following order of reactivity is observed, depending on the type of the alkoxy substituents at the phosphorus atom [51] ... 

The ortho-ester functionalized polymers can be hydrolyzed to the corresponding carboxyl functionalized polymers. Similarly, fimctionalization with the oxiranes, glycidylpropyltrimethoxysilane, 3,4-epoxy-l-butene, and 1,1,1-trifluoro-2,3-epoxypropane has been investigated (195) to prepare trimethoxysilyl functionalized polymers, 1,3-diene fiinctionalized macromonomers, and trifluoromethyl functionalized polsrmers, respectively. Secondary amine functionalized polymers were prepared by termination with iV-(benzylidene)methylamine and also using an iV-benzyl tertiary amine functionalized alkyl lithimn initiator followed by hy-drogenolysis of the benzyl group. 

Chlorotris(triphenylphosphine)rhodium(I) added to a mixture of benzylidene-methylamine and diethylsilane in benzene, stirred 1 hr. at room temp., methanol added, and stirred 10 min. -> benzylmethylamine. Y 95%. F. e. s. I. Ojima, T. Kogure, and Y. Nagai, Tetrah. Let. 1973, 2475. 

Volatile alkyl halogenides such as methyl iodide, methylene chloride etc., react quantitatively with the solid methylamine salt of 5-benzylidene- (39a) [32] and 5,5-diphenylthiohydantoin (37) to form the anticonvulsive solids 225 and 226 in quantitative yield [28] (Scheme 30). Unlike the solution reaction, only the S-alkylation occurs under gas-solid conditions. Furthermore, various dialkylamidodithiolate salts 228 react readily with dichloromethane at 80 °C. The salts with the quaternary cations react at room temperature and it is also possible to catalyze the reaction of the sodium salt by admixture of 10% of the corresponding phase transfer bromides [28]. These reactions have been tuned for removal of dichloromethane from loaded air streams [28]. 

Methoxy-7-methoxycarbonyl-1,2,3,4-tetrahydronaphthalene 2-Naphthalene-carboxylic acid, 5,6,7,8-tetrahydro-3-methoxy-, methyl ester (78112-34-2), 65, 98 Methyl acrylate (96-33-3), 66, 54, 59 dimerization by Pd(II), 66, 52 Methylamine, N-benzylidene-, 65, 140 METHYL 4-0-BENZOYL-6-BROMO-6-DEOXY-a-0-GLUCOPYRANOSIDE ... 

Benzyl-5-(2-hydroxyethyl)-4-methyl-1,3-thiazolium chloride (4568-71-2), 65, 26 N-Benzylidenebenzenesulfonamide (13909-34-7), 66, 203, 204, 206, 210 Benzylidenemalononitrile Malononitrile, benzylidene- Propanedinitrile, (phenylmethylene)- (2700-22-3), 65, 32 Benzyl mercaptan a-Toluenethiol Benzenemethanethiol (100-53-8), 65, 215 N-BENZYL-N-METHOXYMETHYL-N-(TRIMETHYLSlLYL)METHYLAMINE BENZENEMETHANAMINE, N-(METHOXYMETHYL)-N-[(TRlMETHYL-SILYL)METHYL]- (93102-05-7), 67, 133 1-BENZYLOXY-4-PENTEN-2-OL 4-PENTEN-2-OL. 1 -(PHENYLMETHOXY)- (58931-16-11), 69, 80... 

On the other hand, BSMA mines have been tested as precursors to azomethine ylids. When treated with DMAD in the presence of benzoyl chloride, in THF, /V-benzylidene bis(trimethylsilyl)methylamine leads to the formation of iV-benzoyl 2-phenyl-3, 4-dicarbomethoxypyrrole.241... 

The irans-benzylidene derivative (188), obtained as the major product of condensation of 3-methylpiperazine 2,5-dione and benzaldehyde in the presence of acetic anhydride, undergoes photoisomerization to the cis isomer (191) on irradiation in methanol. Both isomers have been converted into tetrahydropyrazine imino ethers (189) and (192) by treatment with triethyloxonium fluoroborate. The trans compound reacts more slowly and gives a lower yield of imino ether and this is attributed to steric hindrance. Compounds 188 and 191 are de-acetylated on treatment with methanolic 2 N potassium hydroxide. The trans and cis isomers (187) and (190), so produced are converted into 3-benzyl-2,5-dihydroxy-6-methylpyrazine (144) when heated at 100° with sodium hydroxide.384 Treatment of the dichloroacetyl derivative of phenylalanine with methylamine gives l-methyl-3-benzylidenepiperazine 2,5-dione with the stereochemistry shown.384a... 

The action of diphenylacetylene on the dimethylaminocarbene complex 393 affords 394, which reacts with benzylidene-A -methylamine in situ to give the bicyclic lactam 395. ... 

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