CN1297534C

CN1297534C - Glycol ester compound for preparing catalyst for olefinic polymerization

Info

Publication number: CN1297534C
Application number: CNB031496997A
Authority: CN
Inventors: 李昌秀; 高明智; 王军; 李现忠; 李天益; 杨菊秀; 李季禹; 刘昆玉
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2003-08-06
Filing date: 2003-08-06
Publication date: 2007-01-31
Anticipated expiration: 2023-08-06
Also published as: CN1580034A

Abstract

The present invention relates to a dihydric alcohol ester compound with the general formula (I) and a preparation method thereof, and an application of the compound in the preparation of olefin polymerization catalysts, wherein R1 and R2 can be identical or different and are selected from straight-chain or branched-chain C1 to C20 alkyl, cycloalkyl, aryl, alkaryl, aralkyl and alkylene or condensed ring aryl. R3 to R6 groups can be identical or different and are selected from hydrogen and halogen or straight-chain or branched-chain C1 to C20 alkyl, cycloalkyl, aryl, alkaryl, aralkyl and alkylene or condensed ring aryl. R<1> and R<2> are selected from hydrogen or straight-chain or branched C1 to C20 alkyl, cycloalkyl, aryl, alkaryl, aralkyl and alkylene or condensed ring aryl, but R<1>, R<2>, R3, R4, R5 and R6 are not hydrogen or halogen wholly at the same time. R<1>, R<2>, R3, R4, R5 and R6 are not formed into rings with each other.

Description

Be used to prepare the diol ester compound of olefin polymerization catalysis

Technical field

The present invention relates to a kind of new dibasic alcohol ester compound, the preparation method of this compound and this compound are used being used for preparing olefin polymerization catalysis.

Technical background

As everyone knows, with magnesium, titanium, halogen and electron donor solid titanium catalyst component, can be used for CH as basal component ₂=CHR olefinic polyreaction, particularly in alpha-olefine polymerizing, can obtain the polymkeric substance of higher yields and higher tacticity with 3 carbon or more carbon atoms, wherein the electron donor compound is one of requisite composition in the catalyst component, and along with the development of internal electron donor compound has caused polyolefin catalyst constantly to update.At present, multiple electron donor compound is disclosed in a large number, for example polycarboxylic acid, monocarboxylic ester or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine etc. and derivative thereof, wherein comparatively commonly used is aromatic carboxylates's class of binary, for example n-butyl phthalate or diisobutyl phthalate etc. can be referring to U.S. Pat 4784983.

In recent years, the electron donor that people attempt to adopt other compound to be used as in the olefin polymerization catalyst components again uses, for example at U.S. Pat 4971937 and the European patent EP 0728769 disclosed catalyst component that is used for olefinic polyreaction, special 1 of two ether groups that contain have been adopted, the 3-diether compound is as electron donor, 2-sec.-propyl-2-isopentyl-1 for example, 3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal and 9,9-two (methoxymethyl) fluorenes etc.At the disclosed ingredient of solid catalyst that is used for olefinic polyreaction of Chinese patent CN1054139A, adopted special 1 of two ketone groups that contain, the 3-cyclohexadione compounds is as electron donor, for example 2,2,4,6,6-pentamethyl--3,5-heptadione and 2,2,6,6-tetramethyl--4-ethyl-3,5-heptadione etc.

The special dibasic aliphatic carboxylic acid ester compound of one class is disclosed again recently, as (referring to WO98/56830, WO98/56834, WO01/57099, WO01/63231 and WO00/55215) such as succinate, malonic ester, glutarates, the use of this class electron donor compound not only can improve activity of such catalysts, and the molecular weight distribution of gained propene polymer is obviously widened.

Yet, the above-mentioned disclosed binary aromatic carboxylic acid's ester compound of above-mentioned employing, contain 1 of two ether groups, the catalyzer that is used for olefinic polymerization of 3-diether compound and the preparation of dibasic aliphatic carboxylic acid ester compound all exists certain defective in actual applications, for example adopt the catalytic activity of catalyzer of binary aromatic carboxylic acid's ester compound lower, and the molecular weight distribution of resulting polymers is also narrower; Adopt 1, though the catalyzer of 3-diether compound is active higher, and catalyzer susceptibility that hydrogen is transferred might as well, the narrow molecular weight distribution of resulting polymers is unfavorable for the exploitation of the different trades mark of polymkeric substance; And adopt the catalytic activity of catalyzer of recent disclosed dibasic aliphatic carboxylicesters still on the low side, and when not adopting the external electron donor component, the degree of isotacticity of resulting polymers is lower.

The inventor has unexpectedly found a kind of polyol ester compound that contains special construction, when it uses as the electron donor in the olefin polymerization catalysis, can obtain the catalyzer of high comprehensive performance, when being used for propylene polymerization, can obtain gratifying polymerization yield rate, and the stereospecificity of polymkeric substance is very high, even when not using external electron donor, still can obtain the polymkeric substance of higher degree of isotacticity, catalyzer is also fine to the susceptibility of hydrogen accent simultaneously, the molecular weight distribution broad of resulting polymers helps the exploitation of the different trades mark of polymkeric substance.It can obtain still less gel content during especially for second third copolymerization at the copolymerization that is used for alkene in addition, therefore has better copolymerization performance.

Summary of the invention

Dibasic alcohol ester compound with following general formula (I):

Wherein:

R ₁And R ₂Can be identical or inequality, be selected from the C of straight or branched ₁-C ₂₀Alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkylene or fused ring aryl, R ₃-R ₆Group can be identical or inequality, is selected from the C of hydrogen, halogen or straight or branched ₁-C ₂₀Alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkylene or fused ring aryl, R ¹And R ²Be selected from the C of hydrogen or straight chain or branching ₁-C ₂₀Alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkylene or fused ring aryl, above-mentioned R ₁-R ₆And R ¹-R ²Optionally in the group comprise one or more halogen atoms as carbon or hydrogen atom or both substituents, but R ¹, R ², R ₃, R ₄, R ₅And R ₆Be not hydrogen or halogen simultaneously entirely, and R ¹, R ², R ₃, R ₄, R ₅And R ₆Cheng Huan not mutually,

Be connected to the R on the same carbon ₃, and R ₄, R ₅And R ₆Respectively organizing at least one in two groups of groups is hydrogen, but can not be hydrogen entirely, when having only one to be not hydrogen altogether in two groups of groups, this is not that the group of hydrogen can not be that halogen replaces or unsubstituted methyl, when having a group to be hydrogen in two groups of groups respectively, two groups can not be all hydrogen or halogen in addition, and possess following restriction simultaneously:

(1) when being not identical group except that methyl for these two for the group of hydrogen, R ¹And R ²Be not hydrogen simultaneously, and work as R ¹And R ²In when having a group to be hydrogen, another group can not with R ₃-R ₆In the identical or R of arbitrary group ₁And R ₂Can not be identical phenyl simultaneously,

(2) when not being methyl for these two, and work as R for the group of hydrogen ¹And R ²Complete be hydrogen or one for hydrogen, when another is methyl, R ₁And R ₂Can not be the phenyl of identical phenyl or halogen or alkyl para-orientation,

(3) when these two when having one to be methyl in the group of hydrogen, another then is not normal-butyl, ethyl, phenyl or isobutyl-or R ¹And R ²Be not hydrogen or R entirely ₁And R ₂Can not be identical bromo phenyl simultaneously.

General formula compound of the present invention preferably, R ₃-R ₆Group is selected from that hydrogen, halogen atom replace or unsubstituted ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl or, the phenyl that replaces of phenyl or alkyl.

Preferably, R ¹And R ²Be selected from the phenyl of hydrogen, halogen atom replacement or unsubstituted methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, allyl group, phenyl or replacement or the phenyl that alkyl replaces.

Preferably, R ₁, R ₂In have at least one to be to contain the group of phenyl ring, phenyl or preferably by C ₁-C ₂₀Alkyl or the phenyl that replaces of halogen atom, more preferably, R ₁, R ₂All are phenyl or by C ₁-C ₂₀Alkyl or the phenyl that replaces of halogen atom.

Preferably, R in general formula (I) compound ₃, R ₄, R ₅And R ₆In to have only a group be not hydrogen, this does not replace or unsubstituted ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl or phenyl for the group of hydrogen is selected from halogen atom.

Preferably, R in general formula (I) compound ₃, and R ₄, R ₅And R ₆Has only a C who is selected from straight or branched in two groups of groups respectively ₁-C ₂₀Alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkylene or fused ring aryl and when identical, R ¹And R ²Be not hydrogen simultaneously, and work as R ¹And R ²In when having a group to be hydrogen, another group is selected from the C of straight or branched ₁-C ₂₀Alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkylene or fused ring aryl but can not with R ₃-R ₆In be not the identical or R of group of hydrogen ₁And R ₂Can not be identical phenyl simultaneously.

In above-mentioned general formula (I) compound, most preferably, be connected to the R on the same carbon ₃And R ₄, R ₅And R ₆In two groups of groups, when one of them group was hydrogen, another group was selected from halogen atom and replaces or unsubstituted ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl or phenyl; R ¹And R ²Identical or different, be selected from hydrogen, halogen atom replacement or unsubstituted methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, allyl group, phenyl, but work as R ₃, and R ₄, R ₅And R ₆Be not that the group of hydrogen is when identical, if R in two groups of groups ¹And R ²Have only a group for hydrogen, this be not hydrogen group can not with R ₃,, R ₄, R ₅And R ₆In be not that the group of hydrogen is identical; R ₁, R ₂All are phenyl or by C ₁-C ₂₀Alkyl or the phenyl that replaces of halogen atom.

Particularly, the dibasic alcohol ester compound of general formula (I) comprising:

2,4-pentanediol two (m-chlorobenzoic acid) ester, 2,4-pentanediol two (o-bromobenzoic acid) ester, 2,4-pentanediol two (p-methylbenzoic acid) ester, 2,4-pentanediol two (p-tert-butyl benzoic acid) ester, 2,4-pentanediol two (to butylbenzoic acid) ester, 2,4-pentanediol phenylformic acid laurate, 2,4-pentanediol two laurates, 6-heptene-2,4-heptanediol dibenzoate, 3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 6-methyl-2,4-heptanediol dibenzoate, 6-methyl-2,4-heptanediol two (Chlorodracylic acid) ester, 6-methyl-2,4-heptanediol two (p-methylbenzoic acid) ester, 6-methyl-2,4-heptanediol two (m-methyl benzoic acid) ester, 6-methyl-2,4-heptanediol two pivalates, 3-methyl-2,4-pentanediol two (Chlorodracylic acid) ester, 3-methyl-2,4-pentanediol two (p-methylbenzoic acid) ester, 3-butyl-2,4-pentanediol two (p-methylbenzoic acid) ester, 3-methyl-2,4-pentanediol two (p-tert-butyl benzoic acid) ester, 3-methyl-2,4-pentanediol one phenylformic acid one laurate, 3,3-dimethyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol one phenylformic acid one laurate, 3-ethyl-2,4-pentanediol dibenzoate, 3-butyl-2,4-pentanediol dibenzoate, 3-allyl group-2,4-pentanediol dibenzoate, 4-methyl-3,5-heptanediol dibenzoate, 2-ethyl-1,3-hexylene glycol dibenzoate, 2,2,4-trimethylammonium-1,3-pentanediol dibenzoate, 4-methyl-3,5-ethohexadiol dibenzoate, 5-methyl-4,6 nonanediol dibenzoates, 1,3-phenylbenzene-2-methyl isophthalic acid, the ammediol dibenzoate, 1,3-phenylbenzene-1, ammediol two n Propanoic acid esters, 1,3-phenylbenzene-2-methyl isophthalic acid, the ammediol dipropionate, 1,3-phenylbenzene-2-methyl isophthalic acid, the ammediol diacetate esters, 1,3-phenylbenzene-2 dibenzoate, 1,3-phenylbenzene-2,2-dimethyl-1, the ammediol dipropionate, 1-phenyl-2-methyl isophthalic acid, 3-butyleneglycol dibenzoate, 1-phenyl-2-methyl isophthalic acid, 3-butyleneglycol two pivalates, 6-heptene-2,4-heptanediol two pivalates, 2,2,4,6,6-pentamethyl--3,5-hexylene glycol dibenzoate, 1,3-di-t-butyl-2-ethyl-1, the ammediol dibenzoate, 1,3-phenylbenzene-1, the ammediol diacetate esters, 1-furans-2-methyl isophthalic acid, 3-butyleneglycol dibenzoate, 1,1-dipropyl acyl-oxygen methyl-3-tetrahydrobenzene, 2-sec.-propyl-2-isopentyl-1, the ammediol dibenzoate, 2-sec.-propyl-2-isopentyl-1, ammediol two Chlorodracylic acid esters, 2-sec.-propyl-2-isopentyl-1, ammediol two m-chlorobenzoic acid esters, 2-sec.-propyl-2-isopentyl-1, ammediol two (anisic acid) ester, 2-sec.-propyl-2-isopentyl-1, ammediol two (p-methylbenzoic acid) ester, 2-sec.-propyl-2-isopentyl-1, ammediol one phenylformic acid one propionic ester, 2-sec.-propyl-2-isopentyl-1, the ammediol dipropionate, 2-sec.-propyl-2-isopentyl-1, the ammediol diacrylate, 2-sec.-propyl-2-isopentyl-1, ammediol two laurates, 2,2-diisobutyl-1, ammediol dibenzoate, 2-sec.-propyl-2-isopentyl-1, ammediol-2,2 '-biphenyl-dicarboxylic acid esters, 2-sec.-propyl-2-isopentyl-1, ammediol-phthalic acid ester, 1,3-di-isopropyl-1,3-glycol two (4-butylbenzoic acid) ester, 1-trifluoromethyl-3-methyl-2,4-pentanediol dibenzoate, 1,1,1-three fluoro-3-methyl-2,4-pentanediol dibenzoate, 4,4,4-Trifluoromethyl-1-(2-naphthalene)-1,3 butylene glycol dibenzoate, 2-methyl-2-ethyl-1, the ammediol dibenzoate, 2, two pairs of fluoro methyl benzoic acid esters of 4-pentanediol, 4,6-nonanediol dibenzoate, 2,4-pentanediol two (2-furancarboxylic acid) ester, 1-phenyl-2-amino-1,3 propylene glycol dibenzoates, 2,2-dimethyl-1, the ammediol dibenzoate, 3-methyl-3-butyl-2,4-pentanediol dibenzoate, 3,6-dimethyl-2,4-heptanediol dibenzoate, 2,2,6,6-tetramethyl--3,5-heptanediol dibenzoate etc.

Dibasic alcohol ester compound of the present invention can be synthetic by various reactions, wherein can be in the presence of corresponding acid or acyl chlorides, and make the dibasic alcohol of general formula (II) carry out esterification and obtain corresponding binary alcohol esters,

HO-CR ₃R ₄-CR ¹R ²-CR ₅R ₆-OH (II)

Wherein: R ₃-R ₆, R ¹-R ²Definition such as the definition in the general formula (I).

The synthetic of the dibasic alcohol of general formula (II) can be referring to the document of prior art, for example 9, two (methylol) fluorenes of 9-are (referring to Acta Chemica Scandina-vica 21,1967, pp.718-720), also can be referring to the preparation method of disclosed dibasic alcohol among the Chinese patent CN1141285A.

Dibasic alcohol ester compound of the present invention can be applicable to prepare the catalyzer of olefinic polymerization, and for example the internal electron donor as the catalyst activity component uses.Gained catalyzer high comprehensive performance when being used for propylene polymerization, can obtain gratifying polymerization yield rate, and the stereospecificity of polymkeric substance is very high, and the molecular weight distribution broad of resulting polymers helps the exploitation of the different trades mark of polymkeric substance.

Embodiment

Embodiment given below is for the present invention is described, rather than limits the invention.

Testing method:

1, fusing point: adopt XT4A micro melting point apparatus (temperature control type).

2, the mensuration of nucleus magnetic resonance: use Bruke dmx300 nmr determination ¹H-NMR (300MHz, solvent C DCl ₃, TMS is interior mark, measures temperature 300K).

3, molecular weight distribution MWD (MWD=Mw/Mn) employing PL-GPC220 is mensuration (standard specimen: PS, flow velocity: 1.0ml/min, the pillar: 3xPlgel 10umM1xED-B 300 * 7.5nm) of solvent under 150 ℃ with the trichlorobenzene

4, the polymkeric substance degree of isotacticity adopts the heptane extraction process to measure (heptane boiling extracting 6 hours): two gram exsiccant polymer samples, be placed in the extractor with the extracting of boiling heptane after 6 hours, the polymer weight (g) that residuum is dried to the constant weight gained is degree of isotacticity with 2 ratio.

Synthesizing of compound

Embodiment 1

2, the preparation of 4-pentanediol two (m-chlorobenzoic acid) ester

0.03mol 2, add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add the 0.075mol m-chlorobenzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless viscous liquid 2,4-pentanediol two (m-chlorobenzoic acid) ester, yield 95%.

2,4-pentanediol two (m-chlorobenzoic acid) ester ¹H NMR (TMS, CDCl ₃, ppm): δ 1.3～1.4 (6H, d, methyl H), δ 1.9～2.3 (2H, m, methylene radical H), δ 5.2～5.3 (2H, m, the methyne H of ester group), δ 7.3～8.1 (8H, m, phenyl ring H).

Embodiment 2

2, the preparation of 4-pentanediol two (o-bromobenzoic acid) ester

0.03mol 2, add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add the adjacent bromo-benzoyl chloride of 0.075mol, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 2,4-pentanediol two (o-bromobenzoic acid) ester, yield 90%.

2,4-pentanediol two (o-bromobenzoic acid) ester ¹H NMR (TMS, CDCl ₃, ppm): δ 1.3～1.4 (6H, m, methyl H), δ 2.06～2.09 (2H, d, methylene radical H), δ 5.2～5.3 (2H, m, the methyne H of ester group), δ 7.3～7.9 (8H, m, phenyl ring H).

Embodiment 3

2, the preparation of 4-pentanediol two (p-methylbenzoic acid) ester

0.03mol 2, add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add 0.075mol to methyl benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 2,4-pentanediol two (p-methylbenzoic acid) ester, yield 90%.

2,4-pentanediol two (p-methylbenzoic acid) ester ¹H NMR (TMS, CDCl ₃, ppm): 1.3～1.4 (6H, d, methyl H), 2.0～2.1 (2H, t, methylene radical H), 2.3～2.4 (6H, m, methylene radical H), 5.2～5.3 (2H, m, the methyne H of ester group), 7.1～8.0 (8H, m, phenyl ring H).

Embodiment 4

2, the preparation of 4-pentanediol two (p-tert-butyl benzoic acid) ester

0.03mol 2, add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add 0.075mol to tert.-butylbenzene formyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 2,4-pentanediol two (p-tert-butyl benzoic acid) ester, yield 90%.

2,4-pentanediol two (p-tert-butyl benzoic acid) ester ¹H NMR (TMS, CDCl ₃, ppm): 1.1～1.4 (24H, m, methyl H), 2.0～2.1 (2H, m, methylene radical H), 5.2～5.4 (2H, m, the methyne H of ester group), 7.4～8.1 (8H, m, phenyl ring H).

Embodiment 5

2, the preparation of 4-pentanediol two (aligning butylbenzoic acid) ester

0.03mol 2, add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add 0.075mol to n-butylbenzene formyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 2,4-pentanediol two (aligning butylbenzoic acid) ester, yield 90%.

2,4-pentanediol two (aligning butylbenzoic acid) ester ¹H NMR (TMS, CDCl ₃, ppm): 0.91～0.98 (6H, m, the methyl H of butyl), 1.3～1.4 (8H, m, the methylene radical H of butyl), 1.5～1.6 (6H, m, methyl H), 2.0～2.1 (2H, t, methylene radical H), 2.6～2.7 (4H, t, the methylene radical H of butyl), 5.2～5.3 (2H, m, the methyne H of ester group), 7.1～8.0 (8H, m, phenyl ring H).

Embodiment 6

2, the preparation of 4-pentanediol one phenylformic acid one laurate

0.03mol 2, add 30ml tetrahydrofuran (THF) and 0.04mol pyridine in the 4-pentanediol, under agitation add the 0.03mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml tetrahydrofuran (THF) and 0.05mol pyridine, under agitation adds the 0.04mol cinnamyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 2,4-pentanediol phenylformic acid laurate, yield 89%.

2,4-pentanediol phenylformic acid laurate ¹H NMR (TMS, CDCl ₃, ppm): 0.8～1.4 (6H, m, methyl H), 1.9～2.1 (2H, m, methylene radical H), 5.1～5.3 (2H, m, the methyne H of ester group), 6.2～8.0 (12H, m, phenyl ring and two key H).

Embodiment 7

2, the preparation of 4-pentanediol two laurates

0.03mol 2, add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add the 0.075mol cinnamyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless viscous liquid 2,4-pentanediol two laurates, yield 88%.

2,4-pentanediol two laurates ¹H NMR (TMS, CDCl ₃, ppm): 1.2～1.3 (6H, m, methyl H), 2.0～2.1 (2H, d, methylene radical H), 5.1～5.2 (2H, m, the methyne H of ester group), 6.3～7.6 (14H, m, phenyl ring and two key H).

Embodiment 8

The preparation of 1,3 butylene glycol dibenzoate

0.03mol add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 1,3 butylene glycol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid l, 3-butyleneglycol dibenzoate, yield 95%. ¹HNMR (TMS, CDCl ₃, ppm): δ 1.43～1.45 (3H, d, methyl H), 2.0～2.1 (2H, m, methylene radical H), 4.3～4.4 (2H, m, the methylene radical H of ester group), 5.38～5.43 (1H, m, the methyne H of ester group), 7.3～8.0 (10H, m, phenyl ring H).

Embodiment 9

6-heptene-2,4-heptanediol dibenzoate synthetic

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 2 successively, 4-dihydroxyl-6-heptene, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride.Be added dropwise to complete post-heating backflow 8hr, normal temperature continues reaction 12hr down.After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated gets the 5.1g product.

6-heptene-2,4-heptanediol dibenzoate ¹H-NMR (TMS, CDCl ₃, ppm): 7.8 (10H, aromatic hydrocarbons), 5.6 (H ,=CH-), 5.1 (2H, CH), 4.8 (2H ,=CH ₂), 2.2 (2H, CH ₂), 1.7 (2H, CH ₂), 1.2 (3H, CH ₃).

Embodiment 10

3, the preparation of 5-heptanediol dibenzoate

The preparation of (1) 3,5-heptanediol

14.2g 3,5-heptadione and 30ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 2.5g sodium borohydride, 0.05g sodium hydroxide and 25ml water.Finish, removal of solvent under reduced pressure is with 40ml ethyl acetate continuous extraction 15h.Remove and desolvate, get white solid 3,5-heptanediol, yield 90%.The IR spectrogram is at 3400cm ^-1There is strong absorption peak at the place, and at 1700cm ^-1About do not have absorption peak, prove that reduction reaction carries out fully.m.p.60～65℃。

The preparation of (2) 3,5-heptanediol dibenzoates

0.03mol 3, add 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 5-heptanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless viscous liquid 3,5-heptanediol dibenzoate, yield 92%.

3,5-heptanediol dibenzoate ¹H NMR (TMS, CDCl ₃, ppm): 0.9～1.0 (6H, m, methyl H), 1.7～1.8 (4H, m, the methylene radical H of ethyl), 2.0～2.1 (2H, m, methylene radical H), 5.21～5.27 (2H, m, the methyne H of ester group), 7.3～8.1 (10H, m, phenyl ring H).

Embodiment 11

2,6-dimethyl-3, the preparation of 5-heptanediol dibenzoate

(1) 2,6-dimethyl-3, the preparation of 5-heptanediol

14.2g 2,6-dimethyl-3,5-heptadione and 30ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 2.5g sodium borohydride, 0.05g sodium hydroxide and 25ml water.Finish, removal of solvent under reduced pressure is with 40ml ethyl acetate continuous extraction 15h.Remove and desolvate, underpressure distillation is collected cut and is got colourless liquid 2,6-dimethyl-3,5-heptanediol, yield 90%.The IR spectrogram is at 3400cm ^-1There is strong absorption peak at the place, and at 1700cm ^-1About do not have absorption peak, prove that reduction reaction carries out fully.

(2) 2,6-dimethyl-3, the preparation of 5-heptanediol dibenzoate

0.03mol 2,6-dimethyl-3 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 5-heptanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 2,6-dimethyl-3,5-heptanediol dibenzoate, yield 88%.

2,6-dimethyl-3,5-heptanediol dibenzoate ¹H NMR (TMS, CDCl ₃, ppm): 0.95～0.99 (12H, m, methyl H), 1.9～2.0 (4H, m, methylene radical and methyne H), 5.10～5.17 (2H, m, the methyne H of ester group), 7.2～8.0 (10H, m, phenyl ring H).

Embodiment 12

6-methyl-2, the preparation of 4-heptanediol dibenzoate

(1) 6-methyl-2, the preparation of 4-heptanediol

14.2g 6-methyl-2,4-heptadione and 30ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 2.5g sodium borohydride, 0.05g sodium hydroxide and 25ml water.Finish, removal of solvent under reduced pressure is with 40ml ethyl acetate continuous extraction 15h.Remove and desolvate, underpressure distillation is collected cut and is got colourless liquid 3-methyl-3-butyl-2,4-pentanediol, yield 90%.The IR spectrogram is at 3400cm ^-1There is strong absorption peak at the place, and at 1700cm ^-1About do not have absorption peak, prove that reduction reaction carries out fully.

(2) 6-methyl-2, the preparation of 4-heptanediol dibenzoate

0.03mol 6-methyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-heptanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 6-methyl-2,4-heptanediol dibenzoate, yield 95%.

6-methyl-2,4-heptanediol dibenzoate ¹H NMR (TMS, CDCl ₃, ppm): 0.8～0.9 (6H, m, methyl H), 1.3～1.4 (3H, m, methyl H), 1.4～1.5 (2H, m, methylene radical H), 1.6～1.7 (2H, m, methylene radical H), 1.8～1.9 (1H, m, methyne H), 5.3～5.5 (2H, m, methyne H), 7.2～8.0 (10H, m, phenyl H).

Embodiment 13

6-methyl-2, the preparation of 4-heptanediol two (Chlorodracylic acid) ester

0.03mol 6-methyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-heptanediol, under agitation add the 0.075mol parachlorobenzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 6-methyl-2,4-heptanediol two (Chlorodracylic acid) ester, yield 95%.

6-methyl-2,4-heptanediol two (4-chloro-benzoic acid) ester ¹H NMR (TMS, CDCl ₃, ppm): 0.8～0.9 (6H, m, methyl H), 1.3～1.4 (3H, m, methyl H), 1.4～1.5 (2H, m, methylene radical H), 1.6～1.7 (2H, m, methylene radical H), 1.8～1.9 (1H, m, methyne H), 5.4～5.5 (2H, m, methyne H), 7.3～7.9 (10H, m, phenyl H).

Embodiment 14

6-methyl-2, the preparation of 4-heptanediol two (p-methylbenzoic acid) ester

0.03mol 6-methyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-heptanediol, under agitation add 0.075mol to methyl benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 6-methyl-2,4-heptanediol two (p-methylbenzoic acid) ester, yield 95%.

6-methyl-2,4-heptanediol two (p-methylbenzoic acid) ester ¹H NMR (TMS, CDCl ₃, ppm): 0.8～0.9 (6H, m, methyl H), 1.3～1.4 (3H, m, methyl H), 1.4～1.5 (2H, m, methylene radical H), 1.6～1.7 (2H, m, methylene radical H), 1.8～1.9 (1H, m, methyne H), 2.3～2.4 (6H, m, methylene radical H), 5.2～5.3 (2H, m, the methyne H of ester group), 7.1～8.0 (8H, m, phenyl ring H).

Embodiment 15

6-methyl-2, the preparation of 4-heptanediol two (m-methyl benzoic acid) ester

0.03mol 6-methyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-heptanediol, under agitation add the 0.075mol m-methyl benzoyl formyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 6-methyl-2,4-heptanediol two (m-methyl benzoic acid) ester, yield 95%.

6-methyl-2,4-heptanediol two (m-methyl benzoic acid) ester ¹H NMR (TMS, CDCl ₃, ppm): 0.8～0.9 (6H, m, methyl H), 1.3～1.4 (3H, m, methyl H), 1.4～1.5 (2H, m, methylene radical H), 1.6～1.7 (2H, m, methylene radical H), 1.8～1.9 (1H, m, methyne H), 2.2～2.3 (6H, m, methylene radical H), 5.2～5.3 (2H, m, the methyne H of ester group), 7.0～8.1 (8H, m, phenyl ring H).

Embodiment 16

6-methyl-2, the preparation of 4-heptanediol two pivalates

0.03mol 6-methyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-heptanediol, under agitation add the 0.075mol pivalyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 6-methyl-2,4-heptanediol two pivalates, yield 95%.

6-methyl-2,4-heptanediol two pivalates ¹H NMR (TMS, CDCl ₃, ppm): 0.8～0.9 (6H, d, methyl H), 1.1～1.2 (21H, m, methyl H), 1.5～1.6 (2H, m, methylene radical H), 4.8～5.0 (2H, m, the methyne H of ester group).

Embodiment 17

3-methyl-2, the preparation of 4-pentanediol two (Chlorodracylic acid) ester

0.03mol 3-methyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add the 0.075mol parachlorobenzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 3-methyl-2,4-pentanediol two (Chlorodracylic acid) ester, yield 92%.

3-methyl-2,4-pentanediol two (Chlorodracylic acid) ester ¹H NMR (TMS, CDCl ₃, ppm): 1.0～1.1 (3H, m, methyl H), 1.3～1.4 (6H, m, methyl H), 1.9～2.1 (1H, m, methyne H), 5.1～5.3 (2H, m, the methyne H of ester group), δ 7.3～7.9 (8H, m, phenyl ring H).

Embodiment 18

3-methyl-2, the preparation of 4-pentanediol two (p-methylbenzoic acid) ester

0.03mol 3-methyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add 0.075mol 4-methyl benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets white solid 3-methyl-2,4-pentanediol two (p-methylbenzoic acid) ester, yield 92%.m.p.91～92℃。

3-methyl-2,4-pentanediol two (p-methylbenzoic acid) ester ¹H NMR (TMS, CDCl ₃, ppm): 1.1～1.2 (3H, m, methyl H), 1.3～1.4 (6H, m, methyl H), 2.1～2.2 (1H, m, methyne H), 2.3～2.4 (6H, m, the methyl H of phenyl ring), 5.2～5.3 (2H, m, the methyne H of ester group), 7.1～8.0 (8H, m, phenyl ring H).

Embodiment 19

3-butyl-2, the preparation of 4-pentanediol two (p-methylbenzoic acid) ester

0.03mol 3-butyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add 0.075mol to methyl benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 3-butyl-2,4-pentanediol two (p-methylbenzoic acid) ester, yield 95%.

3-butyl-2,4-pentanediol two (p-methylbenzoic acid) ester ¹H NMR (TMS, CDCl ₃, ppm): 0.8～0.9 (3H, m, methyl H), 1.3～1.4 (6H, m, methyl H), 1.5～1.7 (6H, m, methylene radical H), 1.9～2.0 (1H, m, methyne H), 2.3～2.4 (6H, m, the methyl H of phenyl ring), 5.3～5.4 (2H, m, the methyne H of ester group), 7.0～8.0 (8H, m, phenyl ring H).

Embodiment 20

3-methyl-2, the preparation of 4-pentanediol two (p-tert-butyl benzoic acid) ester

0.03mol 3-methyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add 0.075mol to tert.-butylbenzene formyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 3-methyl-2,4-pentanediol two (p-tert-butyl benzoic acid) ester, yield 90%.

3-methyl-2,4-pentanediol two (p-tert-butyl benzoic acid) ester ¹H NMR (TMS, CDCl ₃, ppm): 1.1～1.4 (27H, m, methyl H), 2.0～2.1 (1H, m, methyne H), 5.2～5.4 (2H, m, the methyne H of ester group), 7.4～8.1 (8H, m, phenyl ring H).

Embodiment 21

3-methyl-2,4-pentanediol two pivalates synthetic

(1) 3-methyl-2, the preparation of 4-diacetylmethane

In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to the 0.06mol methyl ethyl diketone.After dropwising, continue reaction 1hr at normal temperatures.Slowly be added dropwise to the 0.07mol methyl iodide under the normal temperature, after dropwising, continue reaction 48hr at normal temperatures.After reaction was finished, solvent evaporated added an amount of saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, anhydrous sodium sulfate drying.Solvent evaporated gets the 5.8g product.

(2) 3-methyl-2, the preparation of 4-pentanediol

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.024molLiAlH successively ₄, 100mlTHF.Slowly be added dropwise to 0.04mol 3-methyl-2 under the ice-water bath condition, 4-diacetylmethane, normal temperature continue reaction 48hr down.Dropping sodium aqueous solution termination reaction slowly after reaction is finished is filtered, and solid ingredient merges organic phase, anhydrous sodium sulfate drying with anhydrous diethyl ether washing three times.Solvent evaporated gets the 3.0g product.

(3) 3-methyl-2, the preparation of 4-pentanediol two pivalates

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 3-methyl-2 successively, 4-pentanediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride.Be added dropwise to complete post-heating backflow 4hr.After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated gets the 4.3g product.

3-methyl-2,4-pentanediol two pivalate products ¹H NMR (TMS, CDCl ₃, ppm): 4.7～5.1 (2H, CH), 1.7 (H, CH), 0.94～1.25 (27H, CH ₃).

Embodiment 22

3-methyl-2, the preparation of 4-pentanediol one phenylformic acid one laurate

0.03mol 3-methyl-2 adds 30ml tetrahydrofuran (THF) and 0.04mol pyridine in the 4-pentanediol, under agitation add the 0.03mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml tetrahydrofuran (THF) and 0.05mol pyridine, under agitation adds the 0.04mol cinnamyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless viscous liquid 3-methyl-2,4-pentanediol phenylformic acid laurate, yield 86%.

3-methyl-2,4-pentanediol phenylformic acid laurate ¹H NMR (TMS, CDCl ₃, ppm): 0.8～1.4 (9, m, methyl H), 1.9～2.1 (1H, m, methyne H), 5.1～5.3 (2H, m, the methyne H of ester group), 6.2～8.0 (12H, m, phenyl ring and two key H).

Embodiment 23

3,3-dimethyl-2, the preparation of 4-pentanediol dibenzoate

(1) 3,3-dimethyl-2, the preparation of 4-diacetylmethane

0.1mol add the 100ml anhydrous tetrahydro furan in the sodium hydride, at room temperature slowly drip 0.12mol 3-methyl-2, the 4-diacetylmethane.Finish and stir 0.5h, slowly drip 0.12mol methyl iodide, stirring at room 10h then.Add the 20ml water dissolution, ethyl acetate extraction.Remove the back underpressure distillation of desolvating, collect 82～84 ℃/1kPa of cut, yield 98%.

(2) 3,3-dimethyl-2, the preparation of 4-pentanediol

10g 3,3-dimethyl-2, and 4-diacetylmethane and 30ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 2.5g sodium borohydride, 0.05g sodium hydroxide and 25ml water.Finish, removal of solvent under reduced pressure is with 40ml ethyl acetate continuous extraction 15h.Remove and desolvate, underpressure distillation is collected cut and is got colourless liquid 3,3-dimethyl-2,4-pentanediol, yield 90%.The IR spectrogram is at 3400cm ^-1There is strong absorption peak at the place, and at 1700cm ^-1About do not have absorption peak, prove that reduction reaction carries out fully.

(3) 3,3-dimethyl-2, the preparation of 4-pentanediol dibenzoate

0.03mol 3,3-dimethyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 3,3-dimethyl-2,4-pentanediol dibenzoate, yield 95%.

3,3-dimethyl-2,4-pentanediol dibenzoate ¹H NMR (TMS, CDCl ₃, ppm): 1.1～1.2 (6H, m, methyl H), 1.3～1.4 (6H, m, methyl H), 5.2～5.3 (2H, m, the methyne H of ester group), 7.4～8.1 (10H, m, phenyl ring H).

Embodiment 24

3,3-dimethyl-2, the preparation of 4-pentanediol one phenylformic acid one laurate

0.03mol 3,3-dimethyl-2 adds 30ml tetrahydrofuran (THF) and 0.04mol pyridine in the 4-pentanediol, under agitation add the 0.03mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml tetrahydrofuran (THF) and 0.05mol pyridine, under agitation adds the 0.04mol cinnamyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless viscous liquid 3,3-dimethyl-2,4-pentanediol one phenylformic acid one laurate, yield 88%.

3,3-dimethyl-2,4-pentanediol one phenylformic acid one laurate ¹H NMR (TMS, CDCl ₃, ppm): 1.0～1.1 (6H, m, methyl H), 1.2～1.3 (6H, m, methyl H), 5.0～5.2 (2H, m, the methyne H of ester group), 6.3～8.0 (12H, m, phenyl ring and two key H).

Embodiment 25

3-ethyl-2,4-pentanediol dibenzoate synthetic

(1) 3-ethyl-2, the preparation of 4-diacetylmethane

In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively.Under ice-water bath, agitation condition, slowly be added dropwise to the 0.06mol methyl ethyl diketone.After dropwising, continue reaction 1hr under the room temperature.Slowly be added dropwise to the 0.07mol iodoethane under the room temperature, after dropwising, continue reaction 24hr under the room temperature.

After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, an amount of anhydrous diethyl ether extraction three times, and separatory merges organic phase, anhydrous sodium sulfate drying.Solvent evaporated gets the 6.5g product.

(2) 3-ethyl-2, the preparation of 4-pentanediol

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.024molLiAlH successively ₄, 100mlTHF.Slowly be added dropwise to 0.04mol3-ethyl-2 under the ice-water bath condition, the 4-diacetylmethane continues reaction 48hr under the room temperature.Slowly be added dropwise to the aqueous sodium hydroxide solution termination reaction, filter, solid ingredient merges organic phase, anhydrous sodium sulfate drying with anhydrous diethyl ether washing three times.Solvent evaporated gets the 3.4g product.

(3) 3-ethyl-2, the preparation of 4-pentanediol dibenzoate

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 3-ethyl-2 successively, 4-pentanediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride.Be added dropwise to complete post-heating backflow 4hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 5.1g product.

3-ethyl-2,4-pentanediol dibenzoate product ¹H NMR (TMS, CDCl ₃, ppm): 7.25～8.17 (10H, phenyl ring), 5.39～5.47 (2H, CH), 1.80 (H, CH), 1.66 (2H, CH ₂), 1.1～1.42 (9H, CH ₃).

Embodiment 26

3-butyl-2, the preparation of 4-pentanediol dibenzoate

(1) 3-butyl-2, the preparation of 4-pentanediol

14.2g 3-butyl-2,4-diacetylmethane and 30ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 2.5g sodium borohydride, 0.05g sodium hydroxide and 25ml water.Finish, removal of solvent under reduced pressure is with 80ml ethyl acetate continuous extraction 15h.Remove and desolvate, underpressure distillation is collected cut and is got colourless liquid 3-butyl-2,4-pentanediol, yield 90%.The IR spectrogram is at 3400cm ^-1There is strong absorption peak at the place, and at 1700cm ^-1About do not have absorption peak, prove that reduction reaction carries out fully.

(2) 3-butyl-2, the preparation of 4-pentanediol dibenzoate

0.03mol 3-butyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 3-butyl-2,4-pentanediol dibenzoate, yield 95%.

3-butyl-2,4-pentanediol dibenzoate ¹H NMR (TMS, CDCl ₃, ppm): 0.8～0.9 (3H, m, methyl H), 1.3～1.4 (6H, m, methyl H), 1.5～1.6 (6H, m, methylene radical H), 2.0～2.1 (1H, m, methyne H), 5.1～5.3 (2H, m, the methyne H of ester group), 7.2～8.0 (10H, m, phenyl ring H)

Embodiment 27

3-allyl group-2,4-pentanediol dibenzoate synthetic

(1) 3-allyl group-2, the preparation of 4-diacetylmethane

In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to the 0.06mol methyl ethyl diketone.After dropwising, at room temperature continue reaction 1hr.Slowly be added dropwise to the 0.07mol bromopropylene under the room temperature, after dropwising, at room temperature continue reaction 24hr.

After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, anhydrous sodium sulfate drying.Solvent evaporated gets the 7.1g product.

(2) 3-allyl group-2, the preparation of 4-pentanediol

Under the ice-water bath condition, with 0.04mol 3-allyl group-2, the mixed solution of 4-diacetylmethane and 12ml anhydrous methanol slowly is added dropwise in the mixed solution that contains 1g sodium borohydride, 0.02g sodium hydroxide and 10ml water.Removal of solvent under reduced pressure after reaction is finished, anhydrous diethyl ether continuous extraction 24hr under agitation condition.Remove behind the filtration drying desolvate the 3.7g product.

(3) 3-allyl group-2, the preparation of 4-pentanediol dibenzoate

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 3-allyl group-2 successively, 4-pentanediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride.Be added dropwise to complete post-heating backflow 4hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 5.3g product.

3-allyl group-2,4-pentanediol dibenzoate product ¹H NMR (TMS, CDCl ₃, ppm): 7.37～8.13 (10H, aromatic hydrocarbons), 6.0 (2H ,=CH ₂), 5.38 (H, CH), 5.12 (2H, CH), 2.49 (2H, CH ₂), 2.27H (CH), 1.38～1.52 (6H, CH ₃).

Embodiment 28

4-methyl-3, the preparation of 5-heptanediol dibenzoate

(1) 4-methyl-3, the preparation of 5-heptadione

0.02mol add the 100ml anhydrous tetrahydro furan in the sodium hydride, at room temperature slowly drip 0.02mol3, the 5-heptadione.Finish and stir 0.5h, slowly drip 0.04mol methyl iodide, stirring at room 10h then.Add the 20ml water dissolution, separate out white solid.Filter, washing, after the drying white solid 4-methyl-3,5-heptadione, yield 94%, m.p.91～92 ℃.

(2) 4-methyl-3, the preparation of 5-heptanediol

14.2g 4-methyl-3,5-heptadione and 30ml methanol mixture are in the mixing solutions of 0～10 ℃, 2.5g sodium borohydride, 0.05g sodium hydroxide and 25ml water.Finish, removal of solvent under reduced pressure is with 40ml ethyl acetate continuous extraction 15h.Remove and desolvate, underpressure distillation is collected cut and is got colourless liquid 4-methyl-3,5-heptanediol, yield 90%.The IR spectrogram is at 3400cm ^-1There is strong absorption peak at the place, and at 1700cm ^-1About do not have absorption peak, prove that reduction reaction carries out fully.

(3) 4-methyl-3, the preparation of 5-heptanediol dibenzoate

0.03mol 4-methyl-3 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 5-heptanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 4-methyl-3,5-heptanediol dibenzoate, yield 88%.

4-methyl-3,5-heptanediol dibenzoate ¹H NMR (TMS, CDCl ₃, ppm): 0.9～1.0 (6H, m, methyl H), 1.1～1.2 (3H, m, methyl H), 1.7～1.8 (4H, m, the methylene radical H of ethyl), 2.1～2.2 (1H, m, methylene radical H), 5.21～5.27 (2H, m, the methyne H of ester group), 7.3～8.1 (10H, m, phenyl ring H).

Embodiment 29

2-ethyl-1, the preparation of 3-hexylene glycol dibenzoate

0.03mol 2-ethyl-1 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 3-hexylene glycol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 2-ethyl-1,3-hexylene glycol dibenzoate, yield 91%.

2-ethyl-1,3-hexylene glycol dibenzoate ¹H NMR (TMS, CDCl ₃, ppm): 0.9～1.1 (6H, m, methyl H), 1.4～1.6 (6H, m, methylene radical H), 2.2～2.3 (1H, m, methyne H), 4.3～4.5 (2H, m, the methylene radical H of ester group), 5.42～5.44 (2H, m, the methyne H of ester group), 7.3～8.0 (10H, m, phenyl ring H).

Embodiment 30

2,2,4-trimethylammonium-1, the preparation of 3-pentanediol dibenzoate

0.03mol 2,2,4-trimethylammonium-1 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 3-pentanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless viscous liquid 2,2,4-trimethylammonium-1,3-pentanediol dibenzoate, yield 85%.

2,2,4-trimethylammonium-1,3-pentanediol dibenzoate ¹H NMR (TMS, CDCl ₃, ppm): 1.01～1.07 (6H, m, methyl H), 1.1 (6H, d, methyl H), 4.1～4.2 (2H, m, the methylene radical H of ester group), 5.17～5.18 (1H, d, the methyne H of ester group), 7.4～8.0 (10H, m, phenyl ring H).

Embodiment 31

4-methyl-3,5-ethohexadiol dibenzoate synthetic

The preparation of (1) 3,5-acetyl caproyl

Under the anhydrous and oxygen-free nitrogen protection, in the there-necked flask that titration and reflux are housed, add 0.07mol sodium hydride, tetrahydrofuran (THF), ice-water bath successively.Begin to drip the mixed solution of 0.06mol ethyl butyrate and 0.03mol butanone under the agitation condition.Dropwise post-heating backflow 4hr.

Rotary Evaporators solvent evaporated and boiling point were in the component below 120 ℃ after reaction was finished.Remainder adds an amount of saturated aqueous common salt to solid ingredient and just dissolves, and anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.

Solvent evaporated, the final 0.015mol product that gets.

(2) 4-methyl-3, the preparation of 5-acetyl caproyl

In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to 0.06mol 3, the 5-acetyl caproyl.After dropwising, continue reaction 1hr at normal temperatures.Slowly be added dropwise to the 0.07mol methyl iodide under the normal temperature, after dropwising, continue reaction 24hr at normal temperatures.

After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated gets product 0.045mol 4-methyl-3, the 5-acetyl caproyl.

(3) 4-methyl-3, the preparation of 5-ethohexadiol

Under the ice-water bath condition, with 0.04mol 4-methyl-3, the mixed solution of 5-acetyl caproyl and 12ml anhydrous methanol slowly is added dropwise in the mixed solution that contains 1g sodium borohydride, 0.02g sodium hydroxide and 10ml water.Removal of solvent under reduced pressure after reaction is finished, anhydrous diethyl ether continuous extraction 24hr under agitation condition.Remove behind the filtration drying desolvate the 4.6g product.

(4) 4-methyl-3, the preparation of 5-ethohexadiol dibenzoate

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 4-methyl-3 successively, 5-ethohexadiol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride.Be added dropwise to complete post-heating backflow 4hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 0.015mol product.

4-methyl-3,5-ethohexadiol dibenzoate ¹H-NMR (TMS, CDCl ₃, ppm): 7.8 (10H, aromatic hydrocarbons), 5.28 (2H, CH), 1.8 (4H, CH ₂), 1.18 (2H, CH ₂), 1.0 (9H, CH ₃)

Embodiment 32

Synthesizing of 5-methyl-4,6 nonanediol dibenzoate

(1) 4,6 the ninth of the ten Heavenly Stems diketone preparation

Under the anhydrous and oxygen-free nitrogen protection, in the there-necked flask that titration and reflux are housed, add 0.07mol sodium hydride, tetrahydrofuran (THF), ice-water bath successively.Begin to drip the mixed solution of 0.06mol ethyl butyrate and 0.03mol 2 pentanone under the agitation condition.Dropwise post-heating backflow 4hr.

Solvent evaporated and boiling point were in the component below 120 ℃ after reaction was finished.Remainder adds an amount of saturated aqueous common salt to solid ingredient and just dissolves, and anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated, the final 2.6g product that gets.

(2) preparation of 5-methyl-4,6 diketone in the ninth of the ten Heavenly Stems

In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to 0.06mol diketone in 4,6 ninth of the ten Heavenly Stems.After dropwising, continue reaction 1hr under the room temperature.Slowly be added dropwise to the 0.07mol methyl iodide under the room temperature, after dropwising, continue reaction 24hr under the room temperature.

After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated gets product 5-methyl-4,6 diketone in ninth of the ten Heavenly Stems 0.045mol.

(3) preparation of 5-methyl-4,6 nonanediol

Under the ice-water bath condition, the mixed solution of 0.04mol 5-methyl-4,6 nonanediol and 12ml anhydrous methanol slowly is added dropwise in the mixed solution that contains 1g sodium borohydride, 0.02g sodium hydroxide and 10ml water.Removal of solvent under reduced pressure after reaction is finished, anhydrous diethyl ether continuous extraction 24hr under agitation condition.Remove behind the filtration drying desolvate the 5.3g product.

(4) preparation of 5-methyl-4,6 nonanediol dibenzoate

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 5-methyl-4,6 nonanediol, 20mlTHF, 0.06mol pyridine in the reaction flask successively, slowly be added dropwise to the 0.05mol Benzoyl chloride under the agitation condition.Be added dropwise to complete post-heating backflow 4hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 0.014mol product.

5-methyl-4,6-nonanediol dibenzoate ¹H-NMR (TMS, CDCl ₃, ppm): 7.85 (10H, aromatic hydrocarbons), 5.38 (2H, CH), 1.7 (4H, CH ₂), 1.3 (4H, CH ₂), 2.45 (1H, CH), 1.0 (9H, CH ₃).

Embodiment 33

1,3-phenylbenzene-2-methyl isophthalic acid, ammediol dibenzoate synthetic

(1) 1,3-phenylbenzene-2-methyl isophthalic acid, the preparation of 3-propanedione

In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to the 0.06mol diphenylpropane-1,3-dione(DPPO).After dropwising, at room temperature continue reaction 1hr.Slowly be added dropwise to the 0.07mol methyl iodide under the room temperature, after dropwising, continue reaction 24hr under the room temperature.

After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated, recrystallization get the 11g product.

(2) 1,3-phenylbenzene-2-methyl isophthalic acid, the preparation of ammediol

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.024molLiAlH successively ₄, 100mlTHF.Slowly be added dropwise to 0.04mol 1 under the ice-water bath condition, 3-phenylbenzene-2-methyl isophthalic acid, the 3-propanedione continues reaction 48hr under the room temperature.

Slowly be added dropwise to the aqueous sodium hydroxide solution termination reaction, filter, solid ingredient merges organic phase, anhydrous sodium sulfate drying with anhydrous diethyl ether washing three times.Solvent evaporated gets the 5.9g product.

(3) 1,3-phenylbenzene-2-methyl isophthalic acid, the preparation of ammediol dibenzoate

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 1 successively, 3-phenylbenzene-2-methyl isophthalic acid, ammediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride.Be added dropwise to complete post-heating backflow 4hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 7.3g product.

1,3-phenylbenzene-2-methyl isophthalic acid, 3-third dibenzoate ¹H NMR (TMS, CDCl ₃, ppm): 7.5 (20H, aromatic hydrocarbons), 5.93 (2H, CH), 1.24 (H, CH), 0.95 (3H, CH ₃).

Embodiment 34

1,3-phenylbenzene-1, ammediol two n Propanoic acid esters synthetic

(1) 1,3-phenylbenzene-1, the preparation of ammediol

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.024molLiAlH successively ₄, 100mlTHF.Slowly be added dropwise to the 0.04mol diphenylpropane-1,3-dione(DPPO) under the ice-water bath condition, normal temperature continues reaction 48hr down.

Slowly be added dropwise to the aqueous sodium hydroxide solution termination reaction, filter, solid ingredient merges organic phase, anhydrous sodium sulfate drying with anhydrous diethyl ether washing three times.Solvent evaporated gets the 8.2g product.

(2) 1,3-phenylbenzene-1, the preparation of ammediol two n Propanoic acid esters

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 1 successively, 3-phenylbenzene-1, ammediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol propionyl chloride.Be added dropwise to complete post-heating backflow 4hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 5.2g product.

1,3-diphenylprop glycol two n Propanoic acid esters ¹H NMR (TMS, CDCl ₃, ppm): 7.13～7.36 (10H, aromatic hydrocarbons), 5.76 (2H, CH), 2.5 (4H, CH ₂), 2.11 (2H, CH ₂), 1.1 (6H, CH ₃).

Embodiment 35

1,3-phenylbenzene-2-methyl isophthalic acid, ammediol dipropionate synthetic

(1) 1,3 phenylbenzene-2-methyl isophthalic acid, the preparation of 3-propanedione

(2) 1,3-phenylbenzene-2-methyl isophthalic acid, the preparation of ammediol

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.024molLiAlH successively ₄, 100mlTHF.Slowly be added dropwise to 0.04mol 1 under the ice-water bath condition, 3-phenylbenzene-2-methyl isophthalic acid, 3-propanedione, normal temperature continue reaction 48hr down.

(3) 1,3-phenylbenzene-2-methyl isophthalic acid, the preparation of ammediol dipropionate

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 1 successively, 3-phenylbenzene-2-methyl isophthalic acid, ammediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the positive propionyl chloride of 0.05mol.Be added dropwise to complete post-heating backflow 4hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 5.5g product.

1,3 phenylbenzene-2-methyl isophthalic acid, the ammediol diacetate esters ¹H NMR (TMS, CDCl ₃, ppm): 7.25 (10H, aromatic hydrocarbons), 5.76 (2H, CH), 2.5 (4H, CH ₂), 2.11 (2H, CH ₂), 1.1 (6H, CH ₃).

Embodiment 36

1,3-phenylbenzene-2-methyl isophthalic acid, ammediol diacetate esters synthetic

(2) 1,3-phenylbenzene-2-methyl isophthalic acid, the preparation of ammediol

(3) 1,3-phenylbenzene-2-methyl isophthalic acid, the preparation of ammediol diacetate esters

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 1 successively, 3-phenylbenzene-2-methyl isophthalic acid, ammediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Acetyl Chloride 98Min..Be added dropwise to complete post-heating backflow 4hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 5.9g product.

1,3-phenylbenzene-2-methyl isophthalic acid, the ammediol diacetate esters ¹H NMR (TMS, CDCl ₃, ppm): 7.3 (10H, aromatic hydrocarbons), 5.6 (2H, CH), 2.4 (1H, CH), 1.0 (9H, CH ₃).

Embodiment 37

1,3-phenylbenzene-2 dibenzoate synthetic

(2) 1,3-phenylbenzene-2,2-dimethyl-1, the preparation of 3-propanedione

In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.06mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to 0.05mol 1,3-phenylbenzene-2-methyl isophthalic acid, 3-propanedione.After dropwising, continue reaction 1hr at normal temperatures.Slowly be added dropwise to the 0.07mol methyl iodide under the normal temperature, after dropwising, continue reaction 24hr at normal temperatures.

After reaction is finished, utilize the Rotary Evaporators solvent evaporated, add saturated aqueous common salt to just in time dissolving fully of solid mixture, an amount of anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated gets the 10g product behind recrystallization.

The preparation of (3) 1,3-phenylbenzene-2

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.024molLiAlH successively ₄, 100mlTHF.Slowly be added dropwise to 0.04mol 1 under the ice-water bath condition, 3-phenylbenzene-2,2-dimethyl-1,3-propanedione, normal temperature continue reaction 48hr down.

Slowly be added dropwise to the aqueous sodium hydroxide solution termination reaction, filter, solid ingredient merges organic phase, anhydrous sodium sulfate drying with anhydrous diethyl ether washing three times.Solvent evaporated gets the 6.2g product.

The preparation of (4) 1,3-phenylbenzene-2 dibenzoate

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 1 successively, 3-phenylbenzene-2, the 2-methyl isophthalic acid, ammediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride.Be added dropwise to complete post-heating backflow 4hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated gets the 7.5g product through column chromatography for separation.

1,3-phenylbenzene-2 dibenzoate ¹H-NMR (TMS, CDCl ₃, ppm): 7.3 (20H, aromatic hydrocarbons), 5.78 (2H, CH), 1.1 (6H, CH ₃).

Embodiment 38

1,3-phenylbenzene-2 dipropionate synthetic

After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated gets the 11g product through recrystallization.

(2) 1,3 phenylbenzene-2,2-dimethyl-1, the preparation of 3-propanedione

After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated gets the 10g product behind recrystallization.

The preparation of (3) 1,3-phenylbenzene-2

The preparation of (4) 1,3-phenylbenzene-2 dipropionate

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 1 successively, 3-phenylbenzene-2,20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol propionyl chloride.Be added dropwise to complete post-heating backflow 4hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 6.4g product.

1,3-phenylbenzene-2 dipropionate ¹H NMR (TMS, CDCl3, ppm): 7.3 (20H, aromatic hydrocarbons), 5.89 (2H, CH), 2.4 (4H, CH ₂), 0.98 (12H, CH ₃).

Embodiment 39

1-phenyl-2-methyl isophthalic acid, 3-butyleneglycol dibenzoate synthetic

(1) 1-phenyl-2-methyl isophthalic acid, the preparation of 3-dimethyl diketone

In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to 0.06mol 1-phenyl-1, the 3-dimethyl diketone.After dropwising, at room temperature continue reaction 1hr.Slowly be added dropwise to the 0.07mol methyl iodide under the room temperature, after dropwising, continue reaction 24hr under the room temperature.

After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated, recrystallization get the 8.5g product.

(2) 1-phenyl-2-methyl isophthalic acid, the preparation of 3-butyleneglycol

Under the ice-water bath condition, with 0.05mol 1-phenyl-2-methyl isophthalic acid, the mixed solution of 3-dimethyl diketone and 15ml anhydrous methanol slowly is added dropwise in the mixed solution that contains 1.25g sodium borohydride, 0.02g sodium hydroxide and 12.5ml water.Removal of solvent under reduced pressure after reaction is finished, anhydrous diethyl ether continuous extraction 24hr under agitation condition.Remove behind the filtration drying desolvate the 7.6g product.

(3) 1-phenyl-2-methyl isophthalic acid, the preparation of 3-butyleneglycol dibenzoate

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 6.5g product.

1-phenyl-2-methyl isophthalic acid, 3-butyleneglycol dibenzoate ¹H-NMR (TMS, CDCl ₃, ppm): 8.2 (15H, aromatic hydrocarbons), 5.6 (2H, CH), 2.1 (H, CH), 1.2 (6H, CH ₃).

Embodiment 40

1-phenyl-2-methyl isophthalic acid, 3-butyleneglycol two pivalates synthetic

(1) 1-phenyl-2-methyl isophthalic acid, the preparation of 3-dimethyl diketone

(2) 1-phenyl-2-methyl isophthalic acid, the preparation of 3-butyleneglycol

(3) 1-phenyl-2-methyl isophthalic acid, the preparation of 3-butyleneglycol two pivalates

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 1 successively, 3-phenylbenzene-2-methyl isophthalic acid, ammediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to 0.05mol tertiary butyl formyl chloride.Be added dropwise to complete post-heating backflow 4hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 5.6g product.

1-phenyl-2-methyl isophthalic acid, 3-butyleneglycol two pivalates ¹H NMR (TMS, CDCl ₃, ppm): 7.3 (5H, aromatic hydrocarbons), 5.6 (2H, CH), 2.1 (H, CH), 1.2 (24H, CH ₃)

Embodiment 41

6-heptene-2,4-heptanediol two pivalates synthetic

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 6-heptene-2 successively, 4-heptanediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to 0.05mol tertiary butyl formyl chloride.Be added dropwise to complete post-heating backflow 4hr.

6-heptene-2,4-heptanediol two pivalates ¹H NMR (TMS, CDCl ₃, ppm): 5.6 (1H ,=CH-), 5.1 (2H, CH), 4.8 (2H ,=CH ₂), 2.2 (2H, CH ₂), 1.7 (2H, CH ₂), 1.2 (24H, CH ₃).

Embodiment 42

1,3-di-t-butyl-2-methyl isophthalic acid, ammediol dibenzoate synthetic

(1) 1,3-di-t-butyl-2-methyl isophthalic acid, the preparation of 3-propanedione

In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to 0.06mol two pivalyl methane.After dropwising, at room temperature continue reaction 1hr.Slowly be added dropwise to the 0.07mol methyl iodide under the room temperature, after dropwising, continue reaction 24hr under the room temperature.

After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated gets the 9.5g product.

(2) 1,3-di-t-butyl-2-methyl isophthalic acid, the preparation of ammediol

Under the ice-water bath condition, the mixed solution of 0.05mol two pivalyl ethane and 12ml anhydrous methanol slowly is added dropwise in the mixed solution that contains 1.25g sodium borohydride, 0.02g sodium hydroxide and 13ml water.Removal of solvent under reduced pressure after reaction is finished, anhydrous diethyl ether continuous extraction 24hr under agitation condition.Remove behind the filtration drying desolvate the 8g product.

(3) 1,3-di-t-butyl-2-methyl isophthalic acid, the preparation of ammediol dibenzoate

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 1 in the reaction flask successively, 3-di-t-butyl-2-methyl isophthalic acid, ammediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride under the agitation condition.Be added dropwise to complete post-heating backflow 4hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 0.016mol product.

1,3-di-t-butyl-2-methyl isophthalic acid, ammediol dibenzoate product ¹H NMR (TMS, CDCl ₃, ppm): 0.0 (10H, aromatic hydrocarbons), 5.3 (2H, CH), 2.1 (H, CH), 1.3 (H, CH ₃).

Embodiment 43

1,3-di-t-butyl-2-ethyl-1, ammediol dibenzoate synthetic

The preparation of (1) two pivalyl propane

In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to 0.06mol two pivalyl methane.After dropwising, at room temperature continue reaction 1hr.Slowly be added dropwise to the 0.07mol iodoethane under the room temperature, after dropwising, continue reaction 24hr under the room temperature.

After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated gets the 10g product.

(2) 1,3-di-t-butyl-2-ethyl-1, the preparation of ammediol

Under the ice-water bath condition, the mixed solution of 0.05mol two pivalyl ethane and 12ml anhydrous methanol slowly is added dropwise in the mixed solution that contains 1.25g sodium borohydride, 0.02g sodium hydroxide and 13ml water.Removal of solvent under reduced pressure after reaction is finished, anhydrous diethyl ether continuous extraction 24hr under agitation condition.Remove behind the filtration drying desolvate the 0.5g product.

(3) 1,3-di-t-butyl-2-ethyl-1, the preparation of ammediol dibenzoate

1,3-di-t-butyl-2-methyl isophthalic acid, ammediol dibenzoate product ¹H NMR (TMS, CDCl ₃, ppm): 8.0 (10H, aromatic hydrocarbons), 5.3 (2H, CH), 2.1 (H, CH), 1.3 (H, CH ₃).

Embodiment 44

1,3-phenylbenzene-1, ammediol diacetate esters synthetic

(1) 1,3-phenylbenzene-1, the preparation of ammediol

Under the ice-water bath condition, the mixed solution of 0.04mol diphenylpropane-1,3-dione(DPPO) and 12ml anhydrous methanol slowly is added dropwise in the mixed solution that contains 1g sodium borohydride, 0.02g sodium hydroxide and 10ml water.Removal of solvent under reduced pressure after reaction is finished, anhydrous diethyl ether continuous extraction 24hr under agitation condition.Remove behind the filtration drying desolvate the 6.8g product.

(2) 1,3-phenylbenzene-1, the preparation of ammediol diacetate esters

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.03mol 1 in the reaction flask successively, 3-phenylbenzene-1, ammediol, 30mlTHF, 0.09mol pyridine slowly are added dropwise to the 0.075mol Acetyl Chloride 98Min. under the agitation condition.Be added dropwise to complete post-heating backflow 4hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 8.4g product.

1,3-phenylbenzene-1, the ammediol diacetate esters ¹HNMR (TMS, CDCl ₃, ppm): 7.13-7.35 (10H, aromatic hydrocarbons), 5.7 (2H, CH), 2.6 (2H, CH ₂), 2.0 (6H, CH ₃).

Embodiment 45

9-fluorenes formic acid-2, the preparation of 4-pentadiol ester

Add 0.06mol 2 in the 250ml flask, 4-pentanediol, 0.05mol 9-fluorenes formic acid and 100ml toluene stir even back and add the 0.2ml vitriol oil, and reflux is also used fraction water device water-dividing.The washing of 15% sodium carbonate solution, saturated common salt is washed to neutrality, tells organic phase, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Re-crystallizing in ethyl acetate gets light yellow tabular crystal 9-fluorenes formic acid-2, the 4-pentadiol ester.Yield 88%, mp＞260 ℃.

9-fluorenes formic acid-2, the 4-pentadiol ester ¹HNMR (TMS, CDCl ₃, ppm): 1.7～1.8 (6H, d, methyl H), 2.4～2.5 (2H, m, methylene radical H), 4.9～5.0 (2H, m, the methylene radical H of ester group), 6.9～7.7 (18H, m, phenyl ring H).

Embodiment 46

3-bromo-2, the preparation of 4-pentanediol dibenzoate

(1) the 3-bromo-2, the preparation of 4-diacetylmethane

In the 250ml flask, add 0.1mol 2,4-diacetylmethane, 0.1mol bromo-succinimide (NBS) and 100ml tetracol phenixin, and add a small amount of Benzoyl Peroxide and do the initiator initiation reaction.Reflux 5h.Cooled and filtered is washed solid with tetracol phenixin.Remove and desolvate, underpressure distillation, the cut of 44～46 ℃/0.7kPa of collection.Yield 70%.

(2) the 3-bromo-2, the preparation of 4-pentanediol

0.07mol 3-bromo-2,4-diacetylmethane and 21ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 1.8g sodium borohydride, 0.1g sodium hydroxide and 18ml water and stir 2h.Removal of solvent under reduced pressure is with 40ml ethyl acetate continuous extraction 15h.Remove and desolvate, column chromatography gets brown liquid 3-bromo-2,4-pentanediol, yield 90%.The IR spectrogram is at 3400cm ^-1There is strong absorption peak at the place, and at 1700cm ^-1About do not have absorption peak, prove that reduction reaction carries out fully.

(3) the 3-bromo-2, the preparation of 4-pentanediol dibenzoate

0.03mol 3-bromo-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets light yellow thick liquid 3-bromo-2,4-pentanediol dibenzoate, yield 88%.

3-bromo-2,4-pentanediol dibenzoate ¹HNMR (TMS, CDCl ₃, ppm): 1.40～1.45 (6H, d, methyl H), 4.3～4.4 (1H, m, methyne H), 5.2～5.3 (2H, m, the methyne H of ester group), 7.4～8.1 (10H, m, phenyl ring H).

Embodiment 47

3-benzyl-2, the preparation of 4-pentanediol dibenzoate

(1) 3-benzyl-2, the preparation of 4-diacetylmethane

Be that negative electrode, 0.05molEtNOTs and 50mlDMF are anodic electrolyzer room temperature electrolysis 10h by 0.075mol 2-Pyrrolidone, 0.075mol tetraethyl-tolysulfonyl ammonium (EtNOTs) and 60ml dimethyl formamide (DMF).Electrode is the platinum electrode of 2cm * 2cm, and electric current is the continuous current of 0.2A.Take out negative solution, slowly drip 0.05mol 2, the 4-diacetylmethane, stirring at room 1h drips the 0.075mol benzyl chloride, stirring at room 5h.Add the saturated NH of 100ml ₄Cl aqueous solution termination reaction, ethyl acetate extraction, anhydrous sodium sulfate drying.Remove and desolvate, underpressure distillation is collected 98～100 ℃/0.5kPa of cut, yield 70%.

(2) 3-benzyl-2, the preparation of 4-pentanediol

1.3g NaBH ₄, 0.1gNaOH and 13ml water slowly drips 15ml methyl alcohol and 0.05mol 3-benzyl-2, the mixed solution of 4-diacetylmethane in the ice bath cooling with under stirring.Finish stirring at room 4h.Removal of solvent under reduced pressure adds ethyl acetate and stirs 12h, filters.Filtrate is used anhydrous sodium sulfate drying after dividing water outlet, removes and desolvates.The IR spectrogram shows nothing-CO-peak and very strong-OH peak is arranged.Yield 95%.

(3) 3-benzyl-2, the preparation of 4-pentanediol dibenzoate

0.03mol 3-benzyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 3 benzyls-2,4-pentanediol dibenzoate, yield 90%.

3-benzyl-2,4-pentanediol dibenzoate ¹HNMR (TMS, CDCl ₃, ppm): 1.3～1.5 (6H, methyl H), 2.3～2.4 (1H, methyne H), 2.9～3.0 (2H, methylene radical H), 5.3～5.4 (2H, the methyne H of ester group), 7.1～8.1 (15H, phenyl ring H).

Embodiment 48

4-propyl group-3, the preparation of 5-heptanediol dibenzoate

(1) 4-propyl group-3, the preparation of 5-heptadione

0.1mol add the 100ml anhydrous tetrahydro furan in the sodium hydride, at room temperature slowly drip 0.1mol 3, the 5-heptadione.Finish and stir 0.5h, slowly drip 0.12mol iodopropane, stirring at room 10h then.Filter, filtrate removing desolvated, and underpressure distillation is collected 64～66 ℃/1.3kPa of cut, yield 75%.

(2) 4-propyl group-3, the preparation of 5-heptanediol

0.07mol4-propyl group-3,5-heptadione and 21ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 1.8g sodium borohydride, 0.1g sodium hydroxide and 18ml water and stir 2h.Removal of solvent under reduced pressure is with 40ml ethyl acetate continuous extraction 15h.Remove and desolvate, column chromatography gets colourless liquid 4-propyl group-3,5-heptanediol, yield 88%.The IR spectrogram is at 3400cm ^-1There is strong absorption peak at the place, and at 1700cm ^-1About do not have absorption peak, prove that reduction reaction carries out fully.

(3) 4-propyl group-3, the preparation of 5-heptanediol dibenzoate

0.03mol 4-propyl group-3 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 5-heptanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless viscous liquid 4-propyl group-3,5-heptanediol dibenzoate, yield 90%.

4-propyl group-3,5-heptanediol dibenzoate ¹HNMR (TMS, CDCl ₃, ppm): 0.8～0.9 (9H, m, methyl H), 1.4～1.6 (4H, m, methylene radical H), 1.7～1.9 (4H, m, methylene radical H), 2.1～2.2 (1H, m, methyne H), 5.2～5.4 (2H, m, the methyne H of ester group), 7.2～8.0 (10H, m, phenyl ring H).

Embodiment 49

4-allyl group-3, the preparation of 5-heptanediol dibenzoate

(1) 4-allyl group-3, the preparation of 5-heptadione

0.1mol add the 100ml anhydrous tetrahydro furan in the sodium hydride, at room temperature slowly drip 0.1mol 3, the 5-heptadione.Finish and stir 0.5h, slowly drip 0.12mol bromopropylene, stirring at room 10h then.Filter, filtrate removing desolvated, and underpressure distillation is collected 60～62 ℃/1.3kPa of cut, yield 80%.

(2) 4-allyl group-3, the preparation of 5-heptanediol

0.08mol 4-allyl group-3,5-heptadione and 24ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 2.0g sodium borohydride, 0.1g sodium hydroxide and 20ml water and stir 2h.Removal of solvent under reduced pressure is with 40ml ethyl acetate continuous extraction 15h.Remove and desolvate, column chromatography gets colourless liquid 4-allyl group-3,5-heptanediol, yield 90%.The IR spectrogram is at 3400cm ^-1There is strong absorption peak at the place, and at 1700cm ^-1About do not have absorption peak, prove that reduction reaction carries out fully.

(3) 4-allyl group-3, the preparation of 5-heptanediol dibenzoate

0.03mol 4-allyl group-3 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 5-heptanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless viscous liquid 4-allyl group-3,5-heptanediol dibenzoate, yield 90%.

4-allyl group-3,5-heptanediol dibenzoate ¹HNMR (TMS, CDCl ₃, ppm): 0.8～0.9 (6H, m, methyl H), 1.7～1.8 (4H, m, methylene radical H), 2.3～2.4 (2H, m, methylene radical H), 5.0～5.2 (3H, m, two key H), 5.8～6.0 (2H, m, the methyne H of ester group), 7.2～8.0 (10H, m, phenyl ring H).

Embodiment 50

4-benzyl-3, the preparation of 5-heptanediol dibenzoate

(1) 4-benzyl-3, the preparation of 5-heptadione

0.1mol add the 100ml anhydrous tetrahydro furan in the sodium hydride, at room temperature slowly drip 0.1mol 3, the 5-heptadione.Finish and stir 0.5h, slowly drip 0.12mol bromobenzyl, stirring at room 10h then.Filter, filtrate removing desolvated, and underpressure distillation is collected 104～106 ℃/1.3kPa of cut, yield 72%.

(2) 4 benzyls-3, the preparation of 5-heptanediol

0.07mol 4-benzyl-3,5-heptadione and 21ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 1.8g sodium borohydride, 0.1g sodium hydroxide and 18ml water and stir 2h.Removal of solvent under reduced pressure is with 40ml ethyl acetate continuous extraction 15h.Remove and desolvate, column chromatography gets colourless sticky solid 4-benzyl-3,5-heptanediol, yield 95%.The IR spectrogram is at 3400cm ^-1There is strong absorption peak at the place, and at 1700cm ^-1About do not have absorption peak, prove that reduction reaction carries out fully.

(3) 4-benzyl-3, the preparation of 5-heptanediol dibenzoate

0.03mol 4-benzyl-3 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 5-heptanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless viscous liquid 4-benzyl-3,5-heptanediol dibenzoate, yield 85%.

4-benzyl-3,5-heptanediol dibenzoate ¹HNMR (TMS, CDCl ₃, ppm): 0.8～0.9 (6H, m, methyl H), 1.7～1.9 (4H, m, methylene radical H), 2.6～2.7 (1H, m, methyne H), 2.8～3.1 (2H, m, methylene radical H), 5.2～5.3 (2H, m, the methyne H of ester group), 7.1～8.0 (15H, m, phenyl ring H).

Embodiment 51

4-bromo-3, the preparation of 5-heptanediol dibenzoate

(1) the 4-bromo-3, the preparation of 5-heptadione

In the 250ml flask, add 0.1mol 3,5-heptadione, 0.1mol bromo-succinimide (NBS) and 100ml tetracol phenixin, and add a small amount of Benzoyl Peroxide and do the initiator initiation reaction.Reflux 5h.Cooled and filtered is washed solid with tetracol phenixin.Remove molten 4 doses, underpressure distillation, the cut of 61～63 ℃/1.3kPa of collection.Yield 75%.

(2) the 4-bromo-3, the preparation of 5-heptanediol

0.07mol 4-bromo-3,5-heptadione and 21ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 1.8g sodium borohydride, 0.1g sodium hydroxide and 18ml water and stir 2h.Removal of solvent under reduced pressure is with 40ml ethyl acetate continuous extraction 15h.Remove and desolvate, column chromatography gets light yellow liquid 4-bromo-3,5-heptanediol, yield 89%.The IR spectrogram is at 3400cm ^-1There is strong absorption peak at the place, and at 1700cm ^-1About do not have absorption peak, prove that reduction reaction carries out fully.

(3) the 4-bromo-3, the preparation of 5-heptanediol dibenzoate

0.03mol 4-bromo-3 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 5-heptanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets light yellow thick liquid 4-bromo-3,5-heptanediol dibenzoate, yield 86%.

4-bromo-3,5-heptanediol dibenzoate ¹HNMR (TMS, CDCl ₃, ppm): 0.9～1.0 (6H, m, methyl H), 1.8～2.0 (4H, m, methylene radical H), 4.1～4.2 (1H, m, methyne H), 5.2～5.4 (2H, m, the methyne H of ester group), 7.4～8.1 (10H, m, phenyl ring H).

Embodiment 52

Synthesizing of 5-ethyl-4,6 nonanediol dibenzoate

(1) 4,6 the ninth of the ten Heavenly Stems diketone preparation

Under the anhydrous and oxygen-free nitrogen protection, in the there-necked flask that titration and reflux are housed, add 0.07mol sodium hydride, tetrahydrofuran (THF), ice-water bath successively.Begin to drip the mixed solution of 0.06mol ethyl butyrate and 0.03mol2-pentanone under the agitation condition.Dropwise post-heating backflow 5hr.

Solvent evaporated and boiling point were in the component below 120 ℃ after reaction was finished.Remainder adds an amount of saturated aqueous common salt to solid ingredient and just dissolves, and anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated, the final 0.014mol product that gets.

(2) preparation of 5-ethyl-4,6 diketone in the ninth of the ten Heavenly Stems

In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to 0.06mol diketone in 4,6 ninth of the ten Heavenly Stems.After dropwising, at room temperature continue reaction 1hr.Slowly be added dropwise to the 0.07mol iodoethane under the room temperature, after dropwising, at room temperature continue reaction 24hr.

After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated gets product 0.045mol.

(3) preparation of 5-ethyl-4,6 nonanediol

Under the ice-water bath condition, the mixed solution of 0.04mol 5-ethyl-4,6 diketone in the ninth of the ten Heavenly Stems and 12ml anhydrous methanol slowly is added dropwise in the mixed solution that contains 1g sodium borohydride, 0.02g sodium hydroxide and 10ml water.Removal of solvent under reduced pressure after reaction is finished, anhydrous diethyl ether continuous extraction 24hr under agitation condition.Remove behind the filtration drying desolvate the 5.8g product.

(4) preparation of 5-ethyl-4,6 nonanediol dibenzoate

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 4-methyl-3 in the reaction flask successively, 5-ethohexadiol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride under the agitation condition.Be added dropwise to complete post-heating backflow 4hr.

1H-NMR (TMS, the CDCl of 5-ethyl-4,6 nonanediol dibenzoate ₃, ppm): 7.85 (10H, aromatic hydrocarbons), 5.38 (2H, CH), 1.9 (2H, CH ₂), 1.7 (4H, CH ₂), 1.3 (4H, CH ₂), 2.45 (1H, CH), 1.0 (9H, CH ₃).

Embodiment 53

3-ethyl-2,4-hexylene glycol dibenzoate

The preparation of (1) 2,4-hexanedione

Under the anhydrous and oxygen-free nitrogen protection, in the there-necked flask that titration and reflux are housed, add 0.07mol sodium hydride, tetrahydrofuran (THF), ice-water bath successively.Begin to drip the mixed solution of 0.06mol ethyl acetate and 0.03mol butanone under the agitation condition.Dropwise post-heating backflow 5hr.

Solvent evaporated, the final 0.012mol product that gets.

(2) 3-ethyl-2, the preparation of 4-hexanedione

In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to 0.06mol 2, the 4-hexanedione.After dropwising, at room temperature continue reaction 1hr.Slowly be added dropwise to the 0.07mol iodoethane under the room temperature, after dropwising, at room temperature continue reaction 24hr.

After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated gets product 0.048mol.

(3) 3-ethyl-2, the preparation of 4-hexylene glycol

Under the ice-water bath condition, with 0.04mol 3-ethyl-2, the mixed solution of 4-hexanedione and 12ml anhydrous methanol slowly is added dropwise in the mixed solution that contains 1g sodium borohydride, 0.02g sodium hydroxide and 10ml water.Removal of solvent under reduced pressure after reaction is finished, anhydrous diethyl ether continuous extraction 24hr under agitation condition.Remove behind the filtration drying desolvate the 5.0g product.

(4) 3-ethyl-2, the preparation of 4-hexylene glycol dibenzoate

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 3-ethyl-2 in the reaction flask successively, 4-hexylene glycol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride under the agitation condition.Be added dropwise to complete post-heating backflow 5hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 6g product.

3-ethyl-2,1H-NMR (TMS, the CDCl of 4-hexylene glycol dibenzoate ₃, ppm): 7.8 (10H, aromatic hydrocarbons), 5.3 (2H, CH), 2.0 (1H, CH), 1.9 (2H, CH ₂), 1.7 (2H, CH ₂), 1.0 (9H, CH ₃).

Embodiment 54

Dibenzoic acid (6-teracrylic acid, 5-glycol) ester

(1) 6-teracrylic acid, the preparation of 5-diketone

Under the anhydrous and oxygen-free nitrogen protection, in the there-necked flask that titration and reflux are housed, add 0.07mol sodium hydride, tetrahydrofuran (THF), ice-water bath successively.Begin to drip the mixed solution of 0.06mol ethyl propenoate and 0.03mol butanone under the agitation condition.Slowly dropwise post-heating backflow 5hr.

Solvent evaporated and boiling point were in the component below 110 ℃ after reaction was finished.Remainder adds an amount of saturated aqueous common salt to solid ingredient and just dissolves, and anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.

Solvent evaporated, the final 0.01mol product that gets.

(2) 6-heptene-4-ethyl-3, the preparation of 5-diketone

In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to 0.06mol 6-teracrylic acid, the 5-diketone.After dropwising, at room temperature continue reaction 1hr.Slowly be added dropwise to the 0.07mol iodoethane under the room temperature, after dropwising, at room temperature continue reaction 24hr.

After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated gets product 0.025mol.

(3) 6-heptene-4-ethyl-3, the preparation of 5-glycol

Under the ice-water bath condition, with 0.04mol 6-heptene-4-ethyl-3, the mixed solution of 5-diketone and 12ml anhydrous methanol slowly is added dropwise in the mixed solution that contains 1g sodium borohydride, 0.02g sodium hydroxide and 10ml water.Removal of solvent under reduced pressure after reaction is finished, anhydrous diethyl ether continuous extraction 24hr under agitation condition.Remove behind the filtration drying desolvate the 5.0g product.

(4) preparation of dibenzoic acid (6-heptene-4-ethyl-3,5-glycol) ester

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 6-heptene-4-ethyl-3 in the reaction flask successively, 5-glycol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride under the agitation condition.Be added dropwise to complete post-heating backflow 4hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 0.013mol product.

1H-NMR (TMS, the CDCl of dibenzoic acid (6-heptene-4-ethyl-3,5-glycol) ester ₃, ppm): 7.8 (10H, aromatic hydrocarbons), 5.3 (2H, CH), 4.0 (3H ,=CH), 2.0 (1H, CH), 1.9 (4H, CH2), 1.0 (6H, CH ₃).

Embodiment 55

4-ethyl-3,5-heptanediol dibenzoate

The preparation of (1) 3,5-heptadione

Under the anhydrous and oxygen-free nitrogen protection, in the there-necked flask that titration and reflux are housed, add 0.07mol sodium hydride, tetrahydrofuran (THF), ice-water bath successively.Begin to drip the mixed solution of 0.06mol ethyl propionate and 0.03mol butanone under the agitation condition.Dropwise post-heating backflow 5hr.

Solvent evaporated and boiling point were in the component below 120 ℃ after reaction was finished.Remainder adds an amount of saturated aqueous common salt to solid ingredient and just dissolves, and anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.

Solvent evaporated, the final 0.014mol product that gets.

(2) 4-ethyl-3, the preparation of 5-heptadione

In the there-necked flask of anhydrous and oxygen-free nitrogen protection, add 0.066mol potassium tert.-butoxide, 150mlTHF successively, open and stir.Under the ice-water bath condition, slowly be added dropwise to 0.06mol 3, the 5-heptadione.After dropwising, at room temperature continue reaction 1hr.Slowly be added dropwise to the 0.07mol iodoethane under the room temperature, after dropwising, at room temperature continue reaction 24hr.

After reaction was finished, solvent evaporated added saturated aqueous common salt to just in time dissolving fully of solid mixture, and an amount of anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated gets product 0.048mol 4-ethyl-3, the 5-heptadione.

(3) 4-ethyl-3, the preparation of 5-heptanediol

Under the ice-water bath condition, with 0.04mol 4-ethyl-3, the mixed solution of 5-heptadione and 12ml anhydrous methanol slowly is added dropwise in the mixed solution that contains 1g sodium borohydride, 0.02g sodium hydroxide and 10ml water.Removal of solvent under reduced pressure after reaction is finished, anhydrous diethyl ether continuous extraction 24hr under agitation condition.Remove behind the filtration drying desolvate the 5.3g product.

(4) 4-ethyl-3, the preparation of 5-heptanediol dibenzoate

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 4-ethyl-3 in the reaction flask successively, 5-heptanediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride under the agitation condition.Be added dropwise to complete post-heating backflow 5hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 6.3g product.

4-ethyl-3,5-heptanediol dibenzoate ¹H-NMR (TMS, CDCl ₃, ppm): 7.8 (10H, aromatic hydrocarbons), 5.3 (2H, CH), 2.0 (1H, CH), 1.9 (2H, CH ₂), 1.7 (4H, CH ₂), 1.0 (9H, CH ₃).

Embodiment 56

2,6-dimethyl-3, the preparation of 5-heptanediol two (4-n-butylbenzene formic acid) ester

0.03mol 2,6-dimethyl-3 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 5-heptanediol, under agitation add 0.075mol 4-n-butylbenzene formyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless viscous liquid 2,6-dimethyl-3,5-heptanediol two (4-n-butylbenzene formic acid) ester, yield 88%.

2,6-dimethyl-3,5-heptanediol two (4-n-butylbenzene formic acid) ester ¹H NMR (TMS, CDCl ₃, ppm): 1.0～1.1 (18H, m, methyl H), 1.3～1.4 (4H, m, methylene radical H), 1.4～1.5 (4H, m, methylene radical H), 1.7～1.8 (2H, m, methyne H), 2.75～2.79 (4H, m, methylene radical H), 2.81～2.85 (2H, m, methylene radical H), 5.20～5.28 (2H, m, the methyne H of ester group), 7.2～8.1 (8H, m, phenyl ring H)

Embodiment 57

1-trifluoromethyl-3-methyl-2,4-pentanediol dibenzoate

Synthetic method gets product 4.3g with embodiment 2.Raw material: 1-trifluoromethyl-3-methyl-2,4-pentanediol (3.4g), Benzoyl chloride (4g), pyridine (4.5g) and tetrahydrofuran (THF) (70m1).

¹H NMR(TMS，CDCl ₃，ppm)：1.4(6H)，2.2～2.4(2H)，5.1～2.6(1H)，5.8(1H)，7.3～7.9(10H)

Embodiment 58

1,1,1-three fluoro-3-methyl-2,4-pentanediol dibenzoate

Synthetic method gets product 5.2g with embodiment 2.Raw material: 1,1,1-three fluoro-3-methyl-2,4-pentanediol (3.8g), Benzoyl chloride (4.5g), pyridine (4.5g) and tetrahydrofuran (THF) (70ml).

¹H NMR(TMS，CDCl ₃，ppm) ¹H NMR(TMS，CDCl ₃，ppm)：1.4(3H)，2.2～2.4(2H).5.3～2.7(2H)，5.8(1H)，7.3～7.9(10H)

Embodiment 60

4,4,4-Trifluoromethyl-1-(2-naphthalene)-1,3 butylene glycol dibenzoate

With sodium borohydride (25g), sodium hydroxide (5g) mixes with water (1000ml), with ice bath this mixture is cooled off, add 4,4 from dropping funnel, 4-Trifluoromethyl-1-(2-naphthalene)-1, the mixture of 3-dimethyl diketone (1mol) and methyl alcohol (300ml), after adding, room temperature reaction 4 hours.Remove the first alcohol and water, in resistates, add ether continuous extraction 17 hours, tell inorganic back mutually and concentrate organic phase, use column chromatography out product.

With 4,4,4-Trifluoromethyl-1-(2-naphthalene)-2,3-butyleneglycol (5g), Benzoyl chloride (4.4ml), pyridine (5.5g) and tetrahydrofuran (THF) (70ml) mix, and are heated to backflow.After occurring refluxing, kept 4 hours.Reduce to room temperature then, in reaction system, add water till inorganic mutually transparent.Tell organic phase, merge with organic phase with the inorganic back mutually of extracted with diethyl ether.With the organic phase drying, after concentrating, use column chromatography out product with anhydrous sodium sulphate, obtain the 3g product.

¹H NMR(TMS，CDCl ₃，ppm)：1.2～1.6(2H)，2.1～2.4(2H)，7.4～8.3(17H)

Embodiment 61

2, two pairs of fluoro methyl benzoic acid esters of 4-pentanediol

Synthetic method gets product 3.5g with embodiment 2.Raw material: 2,4-pentanediol (2.1g), to fluoro methyl benzoyl chloride (9.2g), pyridine (6g) and tetrahydrofuran (THF) (70ml).

¹H NMR(TMS，CDCl ₃，ppm)：1.4(6H)，1.9～2.2(2H)，5.3～5.4(2H)，7.4～8.2(8H)

Embodiment 62

4,6-nonanediol dibenzoate

(1) 4,6 the ninth of the ten Heavenly Stems diketone preparation

Under the anhydrous and oxygen-free nitrogen protection, in the there-necked flask that titration and reflux are housed, add 0.07mol sodium hydride, tetrahydrofuran (THF), ice-water bath successively.Begin to drip the mixed solution of 0.06mol ethyl butyrate and 0.03mol 2 pentanone under the agitation condition.Dropwise post-heating backflow 5hr.

Solvent evaporated and boiling point were in the component below 120 ℃ after reaction was finished.Remainder adds an amount of saturated aqueous common salt to solid ingredient and just dissolves, and anhydrous diethyl ether extraction three times merges organic phase, and saturated aqueous common salt is fully washed, separatory, anhydrous sodium sulfate drying.Solvent evaporated, the final 0.015mol product that gets.

The preparation of (2) 4,6-nonanediols

Under the ice-water bath condition, with 0.04mol 4, the mixed solution of 6-diketone in the ninth of the ten Heavenly Stems and 12ml anhydrous methanol slowly is added dropwise in the mixed solution that contains 1g sodium borohydride, 0.02g sodium hydroxide and 10ml water.Removal of solvent under reduced pressure after reaction is finished, anhydrous diethyl ether continuous extraction 24hr under agitation condition.Remove behind the filtration drying desolvate the 5.1g product.

The preparation of (3) 4,6-nonanediol dibenzoates

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 4 in the reaction flask successively, 6-nonanediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride under the agitation condition.Be added dropwise to complete post-heating backflow 4hr.

4,6-nonanediol dibenzoate ¹H-NMR (TMS, CDCl ₃, ppm): 8.0 (10H, aromatic hydrocarbons), 5.30 (2H, CH), 1.7 (4H, CH ₂), 1.4 (4H, CH ₂), 2.15 (2H, CH ₂), 0.95 (6H, CH ₃).

Embodiment 63

3-methyl-3-butyl-2, the preparation of 4-pentanediol dibenzoate

(1) 3-methyl-3-butyl-2, the preparation of 4-diacetylmethane

0.1mol add the 100ml anhydrous tetrahydro furan in the sodium hydride, at room temperature slowly drip 0.1mol 3-butyl-2, the 4-diacetylmethane.Finish and stir 0.5h, slowly drip 0.12mol methyl iodide, stirring at room 10h then.Add the 20ml water dissolution, ethyl acetate extraction.Remove the back underpressure distillation of desolvating, collect cut 57～59 /0.3kPa, yield 90%.

(2) 3-methyl-3-butyl-2, the preparation of 4-pentanediol

12g 3-methyl-3-butyl-2,4-diacetylmethane and 30ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 2.5g sodium borohydride, 0.05g sodium hydroxide and 25ml water.Finish, removal of solvent under reduced pressure is with 40ml ethyl acetate continuous extraction 15h.Remove and desolvate, underpressure distillation is collected cut and is got colourless liquid 3-methyl-3-butyl-2,4-pentanediol, yield 90%.The IR spectrogram is at 3400cm ^-1There is strong absorption peak at the place, and at 1700cm ^-1About do not have absorption peak, prove that reduction reaction carries out fully.

(3) 3-methyl-3-butyl-2, the preparation of 4-pentanediol dibenzoate

0.03mol 3-methyl-3-butyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-pentanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 3-methyl-3-butyl-2,4-pentanediol dibenzoate, yield 95%.

3-methyl-3-butyl-2,4-pentanediol dibenzoate ¹H NMR (TMS, CDCl ₃, ppm): 0.8～0.9 (3H ,-CH ₃), 0.9～1.1 (6H ,-CH ₂-), 1.1～1.5 (9H ,-CH ₃), 5.3～5.5 (2H ,-CH-), 7.3～8.0 (10H, ArH).

Embodiment 64

3,6-dimethyl-2, the preparation of 4-heptanediol dibenzoate

(1) 3,6-dimethyl-2, the preparation of 4-heptadione

0.1mol add the 100ml anhydrous tetrahydro furan in the sodium hydride, at room temperature slowly drip 0.1mol 6-methyl-2, the 4-heptadione.Finish and stir 0.5h, slowly drip 0.12mol methyl iodide, stirring at room 10h then.Add the 20ml water dissolution, ethyl acetate extraction.Remove the back underpressure distillation of desolvating, collect 88～90 ℃/1kPa of cut, yield 94%.

(2) 3,6-dimethyl-2, the preparation of 4-heptanediol

14.2g 3,6-dimethyl-2,4-heptadione and 30ml methanol mixture are added drop-wise under 0～10 ℃ in the mixing solutions of 2.5g sodium borohydride, 0.05g sodium hydroxide and 25ml water.Finish, removal of solvent under reduced pressure is with 40ml ethyl acetate continuous extraction 15h.Remove and desolvate, underpressure distillation is collected cut and is got colourless liquid 3,6-dimethyl-2,4-heptanediol, yield 90%.The IR spectrogram is at 3400cm ^-1There is strong absorption peak at the place, and at 1700cm ^-1About do not have absorption peak, prove that reduction reaction carries out fully.

(3) 3,6-dimethyl-2, the preparation of 4-heptanediol dibenzoate

0.03mol 3,6-dimethyl-2 adds 30ml tetrahydrofuran (THF) and 0.09mol pyridine in the 4-heptanediol, under agitation add the 0.075mol Benzoyl chloride, reflux 4h.The cooling back adds 20ml saturated aqueous common salt, ethyl acetate extraction, anhydrous Na ₂SO ₄Drying is removed and is desolvated.Column chromatography gets colourless liquid 3,6-dimethyl-2,4-heptanediol dibenzoate, yield 88%.

3,6-dimethyl-2,4-heptanediol dibenzoate ¹H NMR (TMS, CDCl ₃, ppm): 0.8～0.9 (6H, m, methyl H), 1.0～1.1 (3H, m, methyl H), 1.3～1.4 (3H, m, methyl H), 1.5～1.7 (2H, m, methylene radical H), 1.8～1.9 (1H, m, methyne H), 2.0～2.1 (1H, m, methyne H), 5.1～5.5 (2H, m, the methyne H of ester group), 7.3～8.1 (10H, m, phenyl ring H).

Embodiment 65

2,2,6,6-tetramethyl--3,5-heptanediol dibenzoate synthetic

(1) 2,2,6,6-tetramethyl--3, the preparation of 5-heptanediol

Under the ice-water bath condition, with 0.04mol 2,2,6,6-tetramethyl--3, the mixed solution of 5-heptadione and 12ml anhydrous methanol slowly is added dropwise in the mixed solution that contains 1g sodium borohydride, 0.02g sodium hydroxide and 10ml water.Removal of solvent under reduced pressure after reaction is finished, anhydrous diethyl ether continuous extraction 24hr under agitation condition.Remove behind the filtration drying desolvate the 6.1g product.

(2) 2,2,6,6-tetramethyl--3, the preparation of 5-heptanediol dibenzoate

Under the anhydrous and oxygen-free nitrogen atmosphere, add 0.02mol 2,2,6 in the reaction flask successively, 6-tetramethyl--3,5-heptanediol, 20mlTHF, 0.06mol pyridine slowly are added dropwise to the 0.05mol Benzoyl chloride under the agitation condition.Be added dropwise to complete post-heating backflow 4hr.

After reaction is finished, reaction mixture is filtered anhydrous diethyl ether washing solid ingredient three times.With organic phase saturated aqueous common salt thorough washing, anhydrous sodium sulfate drying behind the separatory.Solvent evaporated, column chromatography for separation get the 6.8g product.

2,2,6,6-tetramethyl--3,5-heptanediol dibenzoate product ¹H NMR (TMS, CDCl ₃, ppm): 8.0 (10H, aromatic hydrocarbons), 5.3 (2H, CH), 2.0 (2H, CH ₂), 1.3 (3H, CH ₃).Adopt embodiment 5,6,12 resulting compounds to be applied to the polymerization reaction of alkene respectively.

1, the preparation of olefins polymerizing solid catalyst component:

In through the abundant metathetical reactor of high pure nitrogen, add magnesium chloride 4.8g successively, toluene 95ml, epoxy chloropropane 4ml, tributyl phosphate (TBP) 12.5ml is warming up to 50 ℃ under stirring, and kept 2.5 hours, solid dissolves fully, adds Tetra hydro Phthalic anhydride 1.4g, continues to keep 1 hour.Solution is cooled to below-25 ℃, drips TiCl in 1 hour ₄56ml slowly is warming up to 80 ℃, separates out solids in temperature-rise period gradually, adds the resulting compound 6mmol of the foregoing description respectively, and holding temperature 1 hour after the filtration, adds toluene 70ml, and the washing secondary obtains solid sediment.Add toluene 60ml then, TiCl ₄40ml is warmed up to 100 ℃, handles two hours, after the venting filtrate, adds toluene 60ml again, TiCl ₄40ml is warmed up to 100 ℃, handles venting filtrate two hours.Add toluene 60ml, boiling attitude washing three times adds hexane 60ml again, and boiling attitude washed twice adds hexane 60ml, after the normal temperature washed twice, obtains ingredient of solid catalyst.

2, propylene polymerization experiment:

The catalyst component of above-mentioned gained is carried out propylene polymerization respectively.The propylene polymerization program is: volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, adds AlEt ₃2.5mmol methylcyclohexyl dimethoxy silane (CHMMS) 0.1mmol adds about 8mg of ingredient of solid catalyst and 1.2L hydrogen that the foregoing description obtains again, feeds liquid propene 2.3L, is warming up to 70 ℃, keeps this temperature 1 hour.Cooling, pressure release obtains the PP powder.Polymerization result is listed in table 1.

Table 1

Embodiment	The dibasic alcohol ester compound kind	Binary alcohol esters content (wt%)	Ti (wt％)	Polymerization activity kgPP/gca t	TII (％)	MWD
Embodiment	The dibasic alcohol ester compound kind	Binary alcohol esters content (wt%)	Ti (wt％)	Polymerization activity kgPP/gca t	TII (％)	MWD	Example 5	2,4-pentanediol two (aligning butylbenzoic acid) ester	22.1	3.1	64.2	98.6	9.7
Example 6	2,4-pentanediol one phenylformic acid one laurate	19.2	2.6	50.1	96.8	7.0	Example 5	2,4-pentanediol two (aligning butylbenzoic acid) ester	22.1	3.1	64.2	98.6	9.7
Example 6	2,4-pentanediol one phenylformic acid one laurate	19.2	2.6	50.1	96.8	7.0	Example 12	6-methyl-2,4-heptanediol dibenzoate	17.6	2	57.9	96.8	5.3

Claims

1, the dibasic alcohol ester compound that has following general formula (I):

Wherein:

R ₁And R ₂Can be identical or inequality, be selected from the C of straight or branched ₁-C ₂₀Alkyl, cycloalkyl, aryl, alkaryl, aralkyl or alkylene, R ₃-R ₆Group can be identical or inequality, is selected from the C of hydrogen, halogen or straight or branched ₁-C ₂₀Alkyl, cycloalkyl, aryl, alkaryl, aralkyl or alkylene, R ¹And R ²Be selected from the C of hydrogen or straight chain or branching ₁-C ₂₀Alkyl, cycloalkyl, aryl, alkaryl, aralkyl or alkylene, above-mentioned R ₁-R ₆And R ¹-R ²Optionally in the group comprise one or more halogen atoms as carbon or hydrogen atom or both substituents, but R ¹, R ², R ₃, R ₄, R ₅And R ₆Be not hydrogen or halogen simultaneously entirely, and R ¹, R ², R ₃, R ₄, R ₅And R ₆Cheng Huan not mutually,

Be connected to the R on the same carbon ₃And R ₄, R ₅And R ₆Respectively organizing at least one in two groups of groups is hydrogen, but can not be hydrogen entirely, when having only one to be not hydrogen altogether in two groups of groups, this is not that the group of hydrogen can not be that halogen replaces or unsubstituted methyl, when having a group to be hydrogen in two groups of groups respectively, two groups can not be all hydrogen or halogen in addition, and possess following restriction simultaneously:

(1) when being not identical, group except that methyl for these two for the group of hydrogen, R ¹And R ²Be not hydrogen simultaneously, and work as R ¹And R ²In when having a group to be hydrogen, another group can not with R ₃-R ₆In the identical or R of arbitrary group ₁And R ₂Can not be identical phenyl simultaneously,

(3) when these two when having one to be methyl in the group of hydrogen, another then is not normal-butyl, ethyl, phenyl or isobutyl-or R ¹And R ²Be not hydrogen or R entirely ¹And R ²Can not be identical bromo phenyl simultaneously.

2, diol ester compound according to claim 1, in its formula of (I), R ₃-R ₆Be selected from the phenyl that hydrogen, halogen atom replacement or unsubstituted ethyl, propyl group, butyl, phenyl or alkyl replace, R ¹And R ²Identical or different, be selected from that hydrogen, halogen atom replace or the phenyl of unsubstituted methyl, ethyl, propyl group, butyl, phenyl or replacement.

3, according to the described diol ester compound of one of claim 1-2, wherein R ₁, R ₂In have at least one to be the group that contains phenyl ring.

4, according to the described diol ester compound of one of claim 1-2, wherein R ₁, R ₂In have at least one to be phenyl or by C ₁-C ₂₀Alkyl or the phenyl that replaces of halogen atom.

5, according to the described diol ester compound of one of claim 1-2, wherein R ₁, R ₂All are phenyl or by C ₁-C ₂₀Alkyl or the phenyl that replaces of halogen atom.

6, R in the diol ester compound according to claim 1, its formula of (I) ₃, and R ₄, R ₅And R ₆In to have only a group be not hydrogen, this does not replace or unsubstituted ethyl, propyl group, butyl or phenyl for the group of hydrogen is selected from halogen atom.

7, R in the diol ester compound according to claim 1, its formula of (I) ₃And R ₄, R ₅And R ₆Has only a C who is selected from straight or branched in two groups of groups respectively ₁-C ₂₀Alkyl, cycloalkyl, aryl, alkaryl, aralkyl or alkylene and when identical, R ¹And R ²Be not hydrogen simultaneously, and work as R ¹And R ²In when having a group to be hydrogen, another group is selected from the C of straight or branched ₁-C ₂₀Alkyl, cycloalkyl, aryl, alkaryl, aralkyl or alkylene but can not with R ₃,-R ₆In be not the identical or R of group of hydrogen ₁And R ₂Can not be identical phenyl simultaneously.

8, diol ester compound according to claim 1 in its formula of (I), is connected to the R on the same carbon ₃And R ₄, R ₅And R ₆In two groups of groups, when one of them group was hydrogen, another group was selected from halogen atom and replaces or unsubstituted ethyl, propyl group, butyl or phenyl; R ¹And R ²Identical or different, be selected from hydrogen, halogen atom replacement or unsubstituted methyl, ethyl, propyl group, butyl, phenyl; But work as R ₃And R ₄, R ₅And R ₆Be not that the group of hydrogen is when identical, if R in two groups of groups ¹Have only a group for hydrogen with R2, this be not hydrogen group can not with R ₃, R ₄, R ₅And R ₆In be not that the group of hydrogen is identical; R ₁, R ₂All are phenyl or by C ₁-C ₂₀Alkyl or the phenyl that replaces of halogen atom.

9, dibasic alcohol ester compound according to claim 1, it is selected from 2,4-pentanediol phenylformic acid laurate, 2,4-pentanediol two laurates, 6-heptene-2,4-heptanediol dibenzoate, 6-methyl-2,4-heptanediol two (m-methyl benzoic acid) ester, 3-butyl-2,4-pentanediol two (p-methylbenzoic acid) ester, 3-methyl-2,4-pentanediol one phenylformic acid one laurate, 3,3-dimethyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol one phenylformic acid one laurate, 3-ethyl-2,4-pentanediol dibenzoate, 3-butyl-2,4-pentanediol dibenzoate, 3-allyl group-2,4-pentanediol dibenzoate, 4-methyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-ethohexadiol dibenzoate, 5-methyl-4,6 nonanediol dibenzoates, 1,3-phenylbenzene-2-methyl isophthalic acid, ammediol dipropionate, 1,3-phenylbenzene-2,2-dimethyl-1, the ammediol dibenzoate, 1,3-phenylbenzene-2,2-dimethyl-1, the ammediol dipropionate, 6-heptene-2,4-heptanediol two pivalates, 1,1,1-three fluoro-3-methyl-2,4-pentanediol dibenzoate, 4,6-nonanediol dibenzoate, 3-methyl-3-butyl-2,4-pentanediol dibenzoate.

10, the preparation method of the described dibasic alcohol ester compound of one of claim 1-9 in the presence of corresponding acid or acyl chlorides, makes the dibasic alcohol of general formula (II) carry out esterification and obtains corresponding binary alcohol esters,

HO-CR ₃R ₄-CR ¹R ²-CR ₅R ₆-OH (II)

11, the application of the described dibasic alcohol ester compound of one of claim 1-9 in the preparation olefin polymerization catalysis.