Method for producing 4-acylimidazole derivatives by oxidation of 4-alkyl- or 4-(arylalkyl)imidazole derivatives.     Hamazaki, Takashi; Ebata, Iwao.  (Kuraray Co, Japan).    Jpn. Kokai Tokkyo Koho  (1995),     4 pp.  CODEN: JKXXAF  JP  07285945  A  19951031  Heisei.   Patent  written in Japanese.    Application: JP  94-75790  19940414.

Derivatives of glyoxaline-4(or 5)-formaldehyde and glyoxaline-4(or 5)-carboxylic acid. A new synthesis of histidine.     Pyman, Frank L.    Wellcome Chem. Res. Labs.,  London,    Journal of the Chemical Society, Transactions  (1916),  109  186-202.  
Abstract

cf. C. A. 6, 2066.  All m. ps. are corr.  Glyoxalineformaldehyde (A), OHC.C:CH.NH.CH:N, is best prepd. from the HOCH2 compd. (B) as follows: 26 g. (B) and 38 g. HNO3 (d. 1.42) are digested in a covered dish on the H2O bath until the evolution of brown fumes is almost complete; the cover is then removed, the liquid evapd., and the cryst. residue dissolved in warm concd. Na2CO3 and allowed to stand, 11.3 g. (A) crystg. out.  On acidifying the filtrate faintly to Me orange and letting stand, 5.1 g. glyoxalinecarboxylic acid (C) sep.  The filtrate from this, evapd. almost dry, taken up with alc., filtered from the salts, and the filtrate concd., evapd., and taken up with warm concd. Na2CO3 deposits an additional 3.1 g. (A).  If (C) is the chief product sought, 17 g. (B) and 100 cc. HNO3 are used, the amt. of (A) sinking to 11% of the theory.  The neutral by-product, m. 300? obtained by Fr.ovrddot.ankel (Beitr. chem. Physiol. Path. 10, 116(1907)) could not have been (A), as he thought, as this m. 173-4?  (A) gives a white ppt. with AgNO3-NH4OH, but does not reduce it on boiling; it gives a dye with NaO3SC6H4N2ONa (D); when boiled with Ac2O and NaOAc it does not give the acrylic acid, but decomps.; phenylhydrazone, on grinding the components together, prisms, m. 199-200?  2.5 g. (A), 4.5 g. BzNHCH2CO2H, 2.5 g. anhydrous NaOAc, ground together and heated 0.5 hr. on the H2O bath with 10 cc. Ac2O, gave 2-phenyl-4-[1-acetylglyoxaline-4(or 5)-methylidene]oxazolone (I), yellow needles, m. 191? partly decompd. by boiling alc., not readily sol. in dil. alkalies or acids, decompd. by hot dil. mineral acids; when boiled with 2% aq. Na2CO3 until completely dissolved, it gives a-benzoylamino-b-glyoxaline-4(or 5)-acrylic acid (E), needles with 1 H2O; after drying at 100? m. 208?(decompn.), reduces aq. KMnO4 in the cold, and gives a red dye with (D); hydrochloride, needles, m. 229?(decompn.); picrate, prisms, m. 212?(decompn.).  9.7 g. (E) in 10 parts H2O were shaken with 10 parts 2% Na-Hg, added gradually during 0.75 hr.
without cooling, and the aq. soln. mixed with 21 cc. 33% aq. NaOH, boiled until NH3 was no longer evolved, and then 10 min. longer.  After bone-blacking and neutralizing to litmus with HCl 3.65 g. benzoyl-dl-histidine (F), BzNH(CO2H)CH.CH2C:CH.NH.CH:N, crystd. out, while an additional 1.3 g. were obtained on concg. the filtrate.  Recrystd. from H2O it gave 4.1 g. prisms with 1 H2O, lost at 115?but not at 100? turns yellow about 235? m. 248?(decompn.), gives a dye with (D); hydrochloride, prisms, m. 232?(decompn.); picrate, needles, m. 226?(decompn.).  Hydrolysis of (F) gave dl-histidine, identified through the dipicrate and the dihydrochloride and compared with these derivs. as synthesized in C. A. 5, 3420.  To a soln. of 1 g. (A) in 2.5 cc. satd. NaHSO3 was added 1 g. KCN in 1.3 cc. H2O.  Heat was evolved, and on cooling, 1.5 g. glyoxaline-4(or 5)-formaldehydecyanohydrin sepd.; after recrystn. from H2O it forms needles, m. 115?(decompn.), unstable.  It was reduced during 1 hr. according to D. R. P. 193,643 by dissolving in 40 cc. of 2.5% aq. HCl and stirring at -5?to 3?while gradually adding 90 g. 40% Na-Hg and enough 5 % aq. HCl (about 120 cc.) to keep the soln. nearly neutral.  The aq. soln. was filtered and mixed with 1 l. cold satd. aq. HOC6H2(NO2)3, giving almost at once in 32% yield, b-hydroxy-b-glyoxaline-4(or 5)-ethylamine dipicrate, plates or spikes with 1 H2O which is not lost at 120? sinters above 165? M. 225?(decompn.); dihydrochloride, C3H3N2.CH(OH)CH2NH2.2HCl, needles, m. 216?(decompn.), gives a dye with (D); chloroplatinate, C5H9ON3.H2PtCl6.3H2O, orange prisms, darkens above 225? decomps. 244?  (C) m. and effervesces at 275?when placed in a bath at 100?and slowly heated, while if placed in a bath at 270?it m. 284?  Glyoxaline is formed in both cases.  Contrary to Knoop (Beitr. chem. Physiol. Path. 10, 111 (1907)), it is difficultly sol. in cold H2O.  Hydrochloride, prisms, effervesces 262? nitrate, prisms, effervesces 200? resolidifies, and m. again about 270?
picrate, plates with 1.5 H2O lost at 100? m. above 195? clear at 215? then effervesces.  In aq. Na2CO3 (C) couples with (D), but its esters do not.  Attempts to form the acid chloride resulted in the recovery of unaltered (C).  Ethyl ester, from the HCl salt, boiled 6 hrs. with alc. HCl, satg. with fresh HCl from time to time, plates, m. 162? methyl ester, plates, m. 156?  In the prepn. of (B) from 2-thiol-4(or 5)-aminomethylglyoxaline and HNO3, after the recrystn. of the (B) as hydrogen oxalate in well formed crystals, the mother liquors deposited a powdery Salt, m. 80-120?  40 g. of this, mixed with excess of Ba(OH)2, filtered, satd. with CO2, filtered, acidified with HCl, evapd. to a sirup, and stirred with abs. alc. gave 7.2 g.  4(or 5)-[glyoxaline-4(or 5)-methyl]glyoxaline-5(or 4)-methyl alcohol dihydrochloride, prisms, m. 178-9? 4.5 g. more being obtained from the mother liquors.  4(or 5)-[Glyoxaline-4(or .5)-methyl]glyoxaline-5(or 4)-methyl alcohol (II), from the HCl salt in H2O with K2CO3, evapn. to dryness, extn. with abs. alc., and treating the residue from this with a little H2O, silky needles with 2 H2O lost at 100? m. 174? hydrogen oxalate, crystals with 1 H2O, after drying, m. and effervesces 165? dipicrate, needles, m. 197-8?  (II) was recovered unchanged after 3 hrs. at 170?with concd. HCl and 3 hrs. at 190?with 50% H2SO4, with (D) it yields a carmine dye, as does the benzoate, needles from H2O with 1.5 H2O, m. 67-8? anhydrous warts from EtOAc, m. 120-1，

Etard试剂，氧化芳香环甲基为醛基，去查有机合成试剂制备手册吧，那上面有Etard试剂的详细制备方法。

SeO2 玩过了吗 嘿嘿

Selenium dioxide is the most common regent used to selectively oxidize an alkyl fragment, and is particularly effective for converting allylic or benzylic C-H fragments to the corresponding allylic alcohol.

甲基可被许多氧化剂如SeO2、铬酸、次卤酸等氧化为醛，特别是与羰基及芳香环相邻的活性甲基更易氧化。其中SeO2的选择性较好，是最常用的氧化方法之一。不过SeO2毒性太大了，通风要好才能做！

1、Vilsmeier反应
2、etard反应
3、sommelet反应
4、oppenauer反应
这几个反应都可以，你可以自己去看看