CN103333104A - Preparation and synthesis method of 2-benzamides pyridinium acetate - Google Patents

Abstract

The invention relates to a preparation and synthesis method of 2-benzamides pyridinium acetate. The synthesis method of the compound comprises the following steps of enabling 2.8839g (0.03mol) of cyanopyridine and 2.195g (0.01mol) of zinc acetate dihydrate to be reacted in 30ml of absolute methanol, heating, backflowing and stirring the mixture for 48h, immediately heat filtering the mixture after the reaction is ended, sealing through a fresh-keeping film after partial liquid is dried in a centrifugal manner, standing at the room temperature, and obtaining pale yellow crystals two days later. The compound has good catalytic performance in the nitrile silicide reaction of benzaldehyde, and the conversion rate can reach 79 percent.

Description

A kind of preparation and synthetic method of 2-formamido group PAA salt

One, technical field

The present invention relates to a kind of preparation and synthetic method of ammonium salt, exactly is a kind of preparation and synthetic method of 2-formamido group PAA salt.

Two, background technology

The synthetic method of ammonium salt has many bibliographical informations.As far back as 1956, J.Chem.Soc. reported the synthetic method of some ammonium salts, and nineteen fifty-nine, J.Am.Chem.Soc. has also reported the synthetic method of ammonium salt class.（1. Surrey, Alexander R.; Lesher, George Y.; Mayer, J. Richard; Webb, Wm. G. Journal of the American Chemical Society (1959), 81 2894-7; 2 . Davis, M. Journal of the Chemical Society (1956), 337-43.）。

The applicant does not obtain the target product title complex in the experiment of synthetic adjacent cyanopyridine and Zinc diacetate dihydrate title complex, but obtained another kind of novel cpd 2-formamido group PAA salt.

Three, summary of the invention

The present invention aims to provide compound 2-formamido group PAA salt, and technical problem to be solved is that one-step synthesis obtains target product.

The alleged 2-formamido group PAA salt of the present invention be by the preparation of adjacent cyanopyridine and Zinc diacetate dihydrate by the compound shown in the following chemical formula:

（Ⅰ） 。

Chemical name: 2-formamido group PAA salt, be called for short compound (I).

This synthetic method comprises synthesizes and separates, described synthetic be 2.8839g(0.03mol) adjacent cyanopyridine and 2.195g(0.01mol) Zinc diacetate dihydrate reacts in the 30ml anhydrous methanol, reflux stirs 48h, heat filtering immediately after reaction finishes, seal with preservative film after being spin-dried for partially liq, leave standstill under the normal temperature, occur flaxen crystal after 2 days.

This reaction mechanism can be speculated as adjacent cyanopyridine under Zinc diacetate dihydrate and methyl alcohol effect, and cyano group at first hydrolysis becomes acid amides, and the acetic acid in rapid and the Zinc diacetate dihydrate forms acetate.

One step of this synthetic method obtains target product, and technology is simple, and is easy to operate.

Four, description of drawings

Fig. 1 is the X-diffraction analysis figure of 2-formamido group PAA salt.

Five, embodiment

The preparation of 2-formamido group PAA salt

Take by weighing 2.8839g(0.03mol) adjacent cyanopyridine and 2.195g(0.01mol) Zinc diacetate dihydrate puts into the 100ml round-bottomed flask, does reaction solvent adding the 30ml anhydrous methanol, and reflux stirs 48h.Heat filtering immediately after reaction finishes is spin-dried for behind the partially liq with the preservative film sealing, leaves standstill under the normal temperature, occurs flaxen crystal after 2 days.Productive rate: 58%; Title complex is carried out data analysis, and with crystal with petroleum ether several times and vacuum-drying, it is as follows to record the ultimate analysis data: theoretical value is C:52.45%; H:6.05%; N:15.29%.Measured value C:52.29%; H:5.57%; N:15.15%;

IR(KBr,pellet): 3234, 1629, 1591，1569，1535，14,86, 1462，1407,1382,1337,1293,

1247,1212,1157,1094,1048,1020,996,849,809，756,704,633。

The crystal data of compound:

Empirical formula C8H11N3 O2

Molecular weight 181.20

Temperature 293 (2) K

Wavelength 0.71073 A

Crystallographic system, spacer triclinic(crystalline)system, P-1

The deg. of unit cell parameters a=7.929 (3) A alpha=104.673(7)

b = 7.948(3) A beta = 114.088（6）deg.

c = 8.4741(3) A gamma = 93.760（7）deg.

Volume 462.9(3) A^3

Electric density 2,1.300Mg/m^3

Absorption correction parameter 0.096 mm^-1

Number of electrons 192 in the unit cell

Crystallographic dimension 0.212x 0.156x 0.121 mm

Scope 2.70 to 25.05 at Theta angle

Index capture range-9＜=h＜=9 of HKL ,-9＜=k＜6 ,-10＜=l＜=10

Collection/independent diffraction data 2522/ 1603 [R (int)=0.0277]

Data integrity degree 98.1 % of theta=30.5

The method Multi Slice Mode of absorption correction

Transmitance 1.0000 and 0.33319 of minimax

The matrix method of least squares of the method F^2 that refine is used

Number/the number of parameters 1063/0/135 of data number/use restriction

The method 1.132 that refine is used

The consistence factor R 1=0.0714 of point diffraction, wR2=0.2251

Can observe the identical factor R 1=0.0783 of diffraction, wR2=0.2351

Absolute configuration parameter 0.03(3)

Maximum summit on the difference Fourier figure and peak valley 0.361 and-0.321e.A^-3

The typical bond distance's data of crystal:

O(1)-C(7) 1.250(3)

O(2)-C(7) 1.263(3)

N(1)-C(5) 1.337(4)

N(1)-C(1) 1.347(4)

N(2)-C(6) 1.315(3)

N(2)-H(2A) 0.94(4)

N(2)-H(2B) 0.85(4)

N(3)-C(6) 1.312(3)

N(3)-H(3A) 0.90(5)

N(3)-H(3B) 0.85(4)

The typical bond angle data of crystal

C(5)-N(1)-C(1) 117.0(3)

C(6)-N(2)-H(2A) 121(2)

C(6)-N(2)-H(2B) 117(2)

H(2A)-N(2)-H(2B) 122(3)

C(6)-N(3)-H(3A) 123(3)

C(6)-N(3)-H(3B) 116(2)

H(3A)-N(3)-H(3B) 120(4)

N(1)-C(1)-C(2) 123.3(3)

N(1)-C(1)-H(1) 118.3

2. the nitrile silicification reaction is used

2-phenyl-2-(three silyloxies) acetonitrile

0.15mmol compound I, phenyl aldehyde 0.1mL, TMSCN 0.3 ml (3.3mmol) adds under 20 ~ 30 C in succession, after 72 hours, with nuclear-magnetism monitoring, its transformation efficiency: 79 %.

Claims (2)

1. A 2-formamido group PAA salt be by adjacent cyanopyridine with the Zinc diacetate dihydrate preparation by the compound shown in the following chemical formula:

   

   （Ⅰ） 。
2. 2. the synthetic method of the described compound of claim 1 (I), comprise and synthesize and separate, it is characterized in that described synthetic be 2.8839g(0.03mol) adjacent cyanopyridine and 2.195g(0.01mol) Zinc diacetate dihydrate reacts in the 30ml anhydrous methanol, reflux stirs 48h, heat filtering immediately after reaction finishes, seal with preservative film after being spin-dried for partially liq, leave standstill under the normal temperature, occur flaxen crystal after 2 days.

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